JP2021037465A

JP2021037465A - Aromatic ring redox photocatalyst having high reduction power

Info

Publication number: JP2021037465A
Application number: JP2019160380A
Authority: JP
Inventors: 隆司小池; Takashi Koike; 直木納戸; Naoki Noto; 諒谷口; Ryo Taniguchi; 慶悟高橋; Keigo Takahashi; 宗隆穐田; Munetaka Akita
Original assignee: Tokyo Institute of Technology NUC
Current assignee: Tokyo Institute of Technology NUC
Priority date: 2019-09-03
Filing date: 2019-09-03
Publication date: 2021-03-11
Anticipated expiration: 2039-09-03
Also published as: JP7341464B2

Abstract

To provide a redox photocatalyst applicable to a wide range of reactions.SOLUTION: The redox photocatalyst comprises a compound represented by the general formula (I) or (II) in the figure. [In the formula, Ar1, Ar2, Ar3, Ar4, Ar5, Ar6, Ar7 and Ar8 each represent a phenyl group or the like; and R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10 each represent a hydrogen atom or the like.]SELECTED DRAWING: None

Description

本発明は、新規な有機分子光レドックス触媒に関する。本発明の光レドックス触媒は、高い還元力と高い触媒活性を有し、様々な酸化還元化学反応の触媒として有用である。 The present invention relates to a novel organic molecular photoredox catalyst. The photoredox catalyst of the present invention has high reducing power and high catalytic activity, and is useful as a catalyst for various redox chemical reactions.

近年、可視光を駆動力とする環境調和型の有機合成ツールとして、光レドックス触媒が注目されている。本発明者はこの光レドックス触媒作用に注目し、トリフルオロメチル化試薬の還元を鍵とするアルケンのトリフルオロメチル化反応を開発した（Y. Yasu, T. Koike, M. Akita, Angew. Chem. Int. Ed., 51, 9567, (2012) ）。有機フッ素化合物は医農薬分野で注目されており、その合成法の開発は重要であるが、一方で従来の手法では、イリジウム等の貴金属を光触媒として用いなければならないという課題があった。 In recent years, optical redox catalysts have been attracting attention as an environment-friendly organic synthesis tool that uses visible light as a driving force. Focusing on this photoredox catalysis, the present inventor has developed a trifluoromethylation reaction of alkenes with the reduction of trifluoromethylation reagents as the key (Y. Yasu, T. Koike, M. Akita, Angew. Chem). . Int. Ed., 51, 9567, (2012)). Organofluorine compounds are attracting attention in the field of medicines and agrochemicals, and the development of a synthetic method thereof is important.

これに対して、本発明者は最近、単純な多環芳香族炭化水素であるペリレンが、ジフルオロメチル化反応において効果的な光レドックス触媒として働くことを見出した（N. Noto, T. Koike, M. Akita, Chem. Sci., 8, 6375, (2017) ）。この結果から、本発明者はπ共役有機化合物が、金属錯体に取って代わる優れた還元触媒として働く可能性を持つと考察した。一方、ペリレンは安定性や還元力の面で改善の余地を有しており、さらにその溶解性の悪さから有効な官能基化が難しいため、触媒としての発展性に乏しかった。そこで比較的大きなπ共役系を持ち、より官能基化の容易なアントラセンを基盤骨格として用いることを着想し、これを用いた有機光レドックス触媒の開発に取り組んだ。その結果、アントラセンの9位及び10位をジアリールアミノ基によって置換した9,10-ビス（ジフェニルアミノ）アントラセン（以下、「BDA」という場合がある。）が優れた還元触媒として働くことを見出した（非特許文献１） In contrast, the inventor recently found that perylene, a simple polycyclic aromatic hydrocarbon, acts as an effective photoredox catalyst in the difluoromethylation reaction (N. Noto, T. Koike, M. Akita, Chem. Sci., 8, 6375, (2017)). From this result, the present inventor considered that the π-conjugated organic compound has a possibility of acting as an excellent reduction catalyst to replace the metal complex. On the other hand, perylene has room for improvement in terms of stability and reducing power, and further, it is difficult to effectively functionalize it due to its poor solubility, so that it has poor developability as a catalyst. Therefore, we came up with the idea of using anthracene, which has a relatively large π-conjugated system and is easier to functionalize, as the base skeleton, and worked on the development of an organic photoredox catalyst using this. As a result, it was found that 9,10-bis (diphenylamino) anthracene (hereinafter, sometimes referred to as "BDA") in which the 9-position and the 10-position of anthracene were substituted with a diarylamino group acts as an excellent reduction catalyst. (Non-Patent Document 1)

Naoki Noto, Yuya Tanaka, Takashi Koike, and Munetaka Akita, ACS Catal. 2018, 8, 9408-9419Naoki Noto, Yuya Tanaka, Takashi Koike, and Munetaka Akita, ACS Catal. 2018, 8, 9408-9419

BDAは、フルオロアルキル化反応を触媒する際、カチオン性または高い求電子性のフルオロアルキル化試薬を選択する必要があるなど、適用できる反応に制限があった。本発明は、このような背景の下、より広範な反応に適用可能な光レドックス触媒を提供することを目的とする。 The BDA has limited applicable reactions, such as the need to select a cationic or highly electrophilic fluoroalkylating reagent when catalyzing a fluoroalkylation reaction. It is an object of the present invention to provide a photoredox catalyst applicable to a wider range of reactions against such a background.

本発明者は、上記課題を解決するため鋭意検討を重ねた結果、BDAのアントラセンをナフタレン又はベンゼンに置き換えた化合物である1,4-ビス（ジフェニルアミノ）ナフタレン（以下、「BDN」という場合がある。）又は1,4-ビス(ジフェニルアミノ)ベンゼン（以下、「BDB」という場合がある。）が、優れた触媒活性を示すと共に、高い還元力を有し、中性または求電子性の低いフルオロアルキル化試薬からラジカルの発生が可能であることを見出した。 As a result of diligent studies to solve the above problems, the present inventor may refer to 1,4-bis (diphenylamino) naphthalene (hereinafter, referred to as "BDN"), which is a compound in which anthracene of BDA is replaced with naphthalene or benzene. Benzene or 1,4-bis (diphenylamino) benzene (hereinafter sometimes referred to as "BDB") has excellent catalytic activity, high reducing power, and is neutral or electrophilic. We have found that it is possible to generate radicals from low fluoroalkylating reagents.

また、本発明者は、BDN及びBDBは、BDAと触媒の作用機序が異なることも見出した（図１）。即ち、BDAを用いた反応では、触媒と基質との相互作用（静的消光）が必要であるが（Naoki Noto, Yuya Tanaka, Takashi Koike, and Munetaka Akita, ACS Catal. 2018, 8, 9408-9419）、BDN及びBDBは、そのような相互作用は不要であり、より広範な基質の活性化可能であることを見出した。
本発明は、以上の知見に基づき完成されたものである。 The present inventor also found that BDN and BDB have a different mechanism of action from BDA (Fig. 1). That is, the reaction using BDA requires interaction between the catalyst and the substrate (static quenching) (Naoki Noto, Yuya Tanaka, Takashi Koike, and Munetaka Akita, ACS Catal. 2018, 8, 9408-9419). ), BDN and BDB have found that such interactions are not required and a wider range of substrates can be activated.
The present invention has been completed based on the above findings.

即ち、本発明は、以下の（１）〜（９）を提供する。
（１）下記の一般式(I)又は一般式(II)
〔式中、Ar¹、Ar²、Ar³、Ar⁴、Ar⁵、Ar⁶、Ar⁷、及びAr⁸は、それぞれ独立して置換基で置換されていてもよいアリール基又は置換基で置換されていてもよいヘテロアリール基を表し、R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、及びR¹⁰は、それぞれ独立して水素原子、ハロゲン原子、置換基で置換されていてもよいアリール基、又は置換基で置換されていてもよいヘテロアリール基を表す。〕
で表される化合物を含むことを特徴とする光レドックス触媒。 That is, the present invention provides the following (1) to (9).
(1) The following general formula (I) or general formula (II)
[In the formula, Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ , Ar ⁷ , and Ar ⁸ are each independently substituted with an aryl group or a substituent which may be substituted with a substituent. Represents a heteroaryl group that may be, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ are independent hydrogen atoms, respectively. Represents a halogen atom, an aryl group optionally substituted with a substituent, or a heteroaryl group optionally substituted with a substituent. ]
A photoredox catalyst comprising a compound represented by.

（２）一般式(I)及び一般式(II)で表される化合物におけるAr¹、Ar²、Ar³、Ar⁴、Ar⁵、Ar⁶、Ar⁷、及びAr⁸が、それぞれ独立して置換基で置換されていてもよいフェニル基であることを特徴とする（１）に記載の光レドックス触媒。 ^{(2) Ar 1} , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ , Ar ⁷ , and Ar ⁸ in the compounds represented by the general formulas (I) and (II) are independent of each other. The photoredox catalyst according to (1), which is a phenyl group which may be substituted with a substituent.

（３）一般式(I)及び一般式(II)で表される化合物におけるAr¹、Ar²、Ar³、Ar⁴、Ar⁵、Ar⁶、Ar⁷、及びAr⁸が、それぞれ独立してフェニル基又は4位、3位、若しくは2位が置換基で置換されているフェニル基であることを特徴とする（１）に記載の光レドックス触媒。 ^{(3) Ar 1} , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ , Ar ⁷ , and Ar ⁸ in the compounds represented by the general formulas (I) and (II) are independent of each other. The photoredox catalyst according to (1), wherein the phenyl group or the phenyl group in which the 4-position, 3-position, or 2-position is substituted with a substituent is used.

（４）一般式(I)及び一般式(II)で表される化合物におけるAr¹、Ar²、Ar³、Ar⁴、Ar⁵、Ar⁶、Ar⁷、及びAr⁸が、それぞれ独立してフェニル基、4-tert-ブチルフェニル基、又は4-フルオロフェニル基であることを特徴とする（１）に記載の光レドックス触媒。 ^{(4) Ar 1} , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ , Ar ⁷ , and Ar ⁸ in the compounds represented by the general formulas (I) and (II) are independent of each other. The photoredox catalyst according to (1), which is a phenyl group, a 4-tert-butylphenyl group, or a 4-fluorophenyl group.

（５）一般式(I)及び一般式(II)で表される化合物におけるR¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、及びR¹⁰が、水素原子であることを特徴とする（１）乃至（４）のいずれかに記載の光レドックス触媒。 ^{(5) R 1} , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ^{10 in the} compounds represented by the general formulas (I) and (II). The photoredox catalyst according to any one of (1) to (4), wherein is a hydrogen atom.

（６）（１）乃至（５）のいずれかに記載の光レドックス触媒の存在下、光照射下で、酸化還元反応により有機化合物を活性化することを特徴とする化合物の製造方法。 (6) A method for producing a compound, which comprises activating an organic compound by a redox reaction in the presence of the photoredox catalyst according to any one of (1) to (5) and under light irradiation.

（７）酸化還元反応が、fac-トリス(2-フェニルピリジン)イリジウム(III)又はトリス(2,2'-ビピリジン)ルテニウム(II)ビス(ヘキサフルオロホスファート)を触媒とする酸化還元反応であることを特徴とする（６）に記載の化合物の製造方法。 (7) The redox reaction is a redox reaction catalyzed by fac-tris (2-phenylpyridine) iridium (III) or tris (2,2'-bipyridine) ruthenium (II) bis (hexafluorophosphate). The method for producing a compound according to (6), which is characterized by the above.

（８）酸化還元反応が、芳香族アルケンのヒドロキシ−モノフルオロメチル化反応又は芳香族ビニルアセテートのモノフルオロアルキル化反応であることを特徴とする（６）に記載の化合物の製造方法。 (8) The method for producing a compound according to (6), wherein the redox reaction is a hydroxy-monofluoromethylation reaction of an aromatic alkene or a monofluoroalkylation reaction of an aromatic vinyl acetate.

（９）光レドックス触媒が、一般式(II)で表される化合物を含む光レドックス触媒であり、酸化還元反応が、クロロベンゼン類の脱塩素化反応であることを特徴とする（６）に記載の化合物の製造方法。 (9) Described in (6), wherein the photoredox catalyst is a photoredox catalyst containing a compound represented by the general formula (II), and the redox reaction is a dechlorination reaction of chlorobenzenes. Method for producing the compound of.

本発明は、新規な光レドックス触媒を提供する。本発明の光レドックス触媒は、還元力と触媒活性が高く、有機フッ素化合物の合成反応を初めとした様々な化学反応の触媒として有用である。 The present invention provides a novel photoredox catalyst. The photoredox catalyst of the present invention has high reducing power and catalytic activity, and is useful as a catalyst for various chemical reactions including the synthesis reaction of organofluorine compounds.

BDA、BDN、及びBDBの作用機序を示す図。The figure which shows the mechanism of action of BDA, BDN, and BDB. BDNと他の触媒の触媒活性を示す図。図中には、左から、フェノチアジン、BDN、ペリレン、fac-[Ir(ppy)₃]、5,10-ジヒドロフェナジン誘導体、BDAのモノフルオロメチル化生成物の収率が示されている。The figure which shows the catalytic activity of BDN and other catalysts. In the figure, from the left, the yields of phenothiazine, BDN, perylene, fac- [Ir (ppy) ₃ ], 5,10-dihydrophenazine derivative, and monofluoromethylated product of BDA are shown.

以下、本発明を詳細に説明する。
本発明において「ハロゲン原子」とは、例えば、フッ素原子、塩素原子、臭素原子、ヨウ素原子である。 Hereinafter, the present invention will be described in detail.
In the present invention, the "halogen atom" is, for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

本発明において「アリール基」とは、例えば、フェニル基、ナフタレン−１−イル基、ナフタレン−２−イル基である。 In the present invention, the "aryl group" is, for example, a phenyl group, a naphthalene-1-yl group, or a naphthalene-2-yl group.

本発明において「ヘテロアリール基」とは、例えば、ピリジニル基（ピリジン−２−イル基、ピリジン−３−イル基、ピリジン−４−イル基）、ピリミジニル基（ピリミジン−２−イル基、ピリミジン−４−イル基、ピリミジン−５−イル基）、フラニル基（フラン−２−イル基、フラン−３−イル基）、チエニル基（チオフェン−２−イル基、チオフェン−３−イル基）、キノリニル基（キノリン−２−イル基、キノリン−３−イル基、キノリン−４−イル基、キノリン−５−イル基、キノリン−６−イル基）である。 In the present invention, the "heteroaryl group" is, for example, a pyridinyl group (pyridin-2-yl group, pyridine-3-yl group, pyridine-4-yl group), pyrimidinyl group (pyrimidine-2-yl group, pyrimidin-). 4-yl group, pyrimidin-5-yl group), furanyl group (fran-2-yl group, furan-3-yl group), thienyl group (thiophen-2-yl group, thiophen-3-yl group), quinolinyl It is a group (quinolin-2-yl group, quinoline-3-yl group, quinoline-4-yl group, quinoline-5-yl group, quinoline-6-yl group).

本発明において「置換基で置換されていてもよいアリール基」及び「置換基で置換されていてもよいヘテロアリール基」における「置換基」とは、例えば、ハロゲン原子、tert-ブチル基、アリール基、ヘテロアリール基である。また、この置換基であるアリール基又はヘテロアリール基が更に置換基（例えば、ハロゲン原子、tert-ブチル基など）で置換されていてもよい。 In the present invention, the "substituted group" in the "aryl group optionally substituted with a substituent" and the "heteroaryl group optionally substituted with a substituent" is, for example, a halogen atom, a tert-butyl group, an aryl. Group, heteroaryl group. Further, the aryl group or heteroaryl group which is the substituent may be further substituted with a substituent (for example, a halogen atom, a tert-butyl group, etc.).

本発明の光レドックス触媒は、上述した一般式(I)又は一般式(II)で表される化合物を含むことを特徴とするものである。 The photoredox catalyst of the present invention is characterized by containing a compound represented by the above-mentioned general formula (I) or general formula (II).

本発明の光レドックス触媒は、通常、一般式(I)又は一般式(II)で表される化合物のみからなるが、他の物質を含んでいてもよい。 The photoredox catalyst of the present invention usually consists of only the compound represented by the general formula (I) or the general formula (II), but may contain other substances.

一般式(I)においてAr¹、Ar²、Ar³、及びAr⁴は、置換基で置換されていてもよいアリール基又は置換基で置換されていてもよいヘテロアリール基を表す。Ar¹、Ar²、Ar³、及びAr⁴は、前記した基であればよいが、好ましくは、置換基で置換されていてもよいフェニル基であり、より好ましくは、フェニル基（無置換フェニル基）、又は4位、3位、若しくは2位が置換基で置換されているフェニル基であり、更に好ましくは、フェニル基又は4位が置換基で置換されているフェニル基であり、特に好ましくは、フェニル基、4-tert-ブチルフェニル基、又は4-フルオロフェニル基である。Ar¹、Ar²、Ar³、及びAr⁴は同一の基であってもよく、異なる基であってもよい。また、Ar¹、Ar²、Ar³、及びAr⁴のすべてが置換基で置換されている基であってもよく、Ar¹、Ar²、Ar³、及びAr⁴の一部だけが置換基で置換されている基であってもよい（例えば、Ar¹とAr⁴だけ、又はAr²とAr³だけが置換基で置換されている基であってもよい。）。 In general formula (I), Ar ¹ , Ar ² , Ar ³ , and Ar ⁴ represent an aryl group that may be substituted with a substituent or a heteroaryl group that may be substituted with a substituent. Ar ¹ , Ar ² , Ar ³ , and Ar ⁴ may be the above-mentioned groups, but are preferably phenyl groups that may be substituted with a substituent, and more preferably a phenyl group (unsubstituted phenyl). Group), or a phenyl group in which the 4-position, 3-position, or 2-position is substituted with a substituent, more preferably a phenyl group or a phenyl group in which the 4-position is substituted with a substituent, particularly preferable. Is a phenyl group, a 4-tert-butylphenyl group, or a 4-fluorophenyl group. Ar ¹ , Ar ² , Ar ³ , and Ar ⁴ may be the same group or different groups. In addition, Ar ¹ , Ar ² , Ar ³ , and Ar ⁴ may all be substituted with substituents, and only a part of ^{Ar 1} , Ar ² , Ar ³ , and Ar ^{4 is a substituent.} It may be a group substituted with a substituent (for example, ^{only Ar 1} and Ar ⁴ or only Ar ² and Ar ³ may be substituted with a substituent).

一般式(II)においてAr⁵、Ar⁶、Ar⁷及びAr⁸は、置換基で置換されていてもよいアリール基又は置換基で置換されていてもよいヘテロアリール基を表す。Ar⁵、Ar⁶、Ar⁷及びAr⁸は、前記した基であればよいが、好ましくは、置換基で置換されていてもよいフェニル基であり、より好ましくは、フェニル基、又は4位、3位、若しくは2位が置換基で置換されているフェニル基であり、更に好ましくは、フェニル基又は4位が置換基で置換されているフェニル基であり、特に好ましくは、フェニル基、4-tert-ブチルフェニル基、又は4-フルオロフェニル基である。Ar⁵、Ar⁶、Ar⁷及びAr⁸は同一の基であってもよく、異なる基であってもよい。また、Ar⁵、Ar⁶、Ar⁷及びAr⁸のすべてが置換基で置換されている基であってもよく、Ar⁵、Ar⁶、Ar⁷及びAr⁸の一部だけが置換基で置換されている基であってもよい（例えば、Ar⁵とAr⁸だけが置換基で置換されている基であってもよい。）。 In general formula (II), Ar ⁵ , Ar ⁶ , Ar ⁷ and Ar ⁸ represent an aryl group that may be substituted with a substituent or a heteroaryl group that may be substituted with a substituent. Ar ⁵ , Ar ⁶ , Ar ⁷ and Ar ⁸ may be the above-mentioned groups, but are preferably phenyl groups which may be substituted with a substituent, and more preferably a phenyl group or the 4-position. It is a phenyl group in which the 3-position or 2-position is substituted with a substituent, more preferably a phenyl group or a phenyl group in which the 4-position is substituted with a substituent, and particularly preferably a phenyl group, 4-. It is a tert-butylphenyl group or a 4-fluorophenyl group. Ar ⁵ , Ar ⁶ , Ar ⁷ and Ar ⁸ may be the same group or different groups. Further, Ar ⁵ , Ar ⁶ , Ar ⁷ and Ar ⁸ may all be substituted with a substituent ^{, and only a part of Ar 5} , Ar ⁶ , Ar ⁷ and Ar ⁸ is substituted with a substituent. It may be a group that has been substituted (for example, it may be a group in which ^{only Ar 5} and Ar ⁸ are substituted with substituents).

一般式(I)においてR¹、R²、R³、R⁴、R⁵、及びR⁶は、水素原子、ハロゲン原子、置換基で置換されていてもよいアリール基、又は置換基で置換されていてもよいヘテロアリール基を表す。R¹、R²、R³、R⁴、R⁵、及びR⁶は、前記した基であればよいが、好ましくは、水素原子又はフッ素原子であり、より好ましくは水素原子である。R¹、R²、R³、R⁴、R⁵、及びR⁶は同一の基であってもよく、異なる基であってもよい。 In general formula (I), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ are substituted with a hydrogen atom, a halogen atom, an aryl group optionally substituted with a substituent, or a substituent. Represents a heteroaryl group which may be present. R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ may be the above-mentioned groups, but are preferably hydrogen atoms or fluorine atoms, and more preferably hydrogen atoms. R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ may be the same group or different groups.

一般式(II)においてR⁷、R⁸、R⁹、及びR¹⁰は、水素原子、ハロゲン原子、置換基で置換されていてもよいアリール基、又は置換基で置換されていてもよいヘテロアリール基を表す。R⁷、R⁸、R⁹、及びR¹⁰は、前記した基であればよいが、好ましくは、水素原子又はフッ素原子であり、より好ましくは水素原子である。R⁷、R⁸、R⁹、及びR¹⁰は同一の基であってもよく、異なる基であってもよい。 In general formula (II), R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ are a hydrogen atom, a halogen atom, an aryl group optionally substituted with a substituent, or a heteroaryl optionally substituted with a substituent. Represents a group. R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ may be the above-mentioned groups, but are preferably hydrogen atoms or fluorine atoms, and more preferably hydrogen atoms. R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ may be the same group or different groups.

一般式(I)で表される化合物は、実施例１に記載した1,4-ジブロモナフタレンとジフェニルアミンを原料とする製造方法に、必要に応じて改変や修正を加えた方法に従って製造できる。例えば、置換基で置換されているフェニル基を有する化合物を製造する場合は、ジフェニルアミンの代わりに、ジフェニルアミンのフェニル基に目的の置換基が導入された化合物を原料として製造すればよい。また、フェニル基以外のアリール基やヘテロアリール基を有する化合物を製造する場合は、ジフェニルアミンの代わりに、ジフェニルアミンのフェニル基がフェニル基以外のアリール基やヘテロアリール基に置き換えられた化合物を原料として製造すればよい。 The compound represented by the general formula (I) can be produced according to the production method using 1,4-dibromonaphthalene and diphenylamine as raw materials described in Example 1, with modifications and modifications as necessary. For example, in the case of producing a compound having a phenyl group substituted with a substituent, a compound in which the desired substituent is introduced into the phenyl group of diphenylamine may be produced as a raw material instead of diphenylamine. When producing a compound having an aryl group other than a phenyl group or a heteroaryl group, a compound in which the phenyl group of diphenylamine is replaced with an aryl group or a heteroaryl group other than the phenyl group is used as a raw material instead of diphenylamine. do it.

一般式(II)で表される化合物は、実施例２に記載した1,4-ジブロモベンゼンとジフェニルアミンを原料とする製造方法に、必要に応じて改変や修正を加えた方法に従って製造できる。例えば、置換基で置換されているフェニル基を有する化合物を製造する場合は、ジフェニルアミンの代わりに、ジフェニルアミンのフェニル基に目的の置換基が導入された化合物を原料として製造すればよい。また、フェニル基以外のアリール基やヘテロアリール基を有する化合物を製造する場合は、ジフェニルアミンの代わりに、ジフェニルアミンのフェニル基がフェニル基以外のアリール基やヘテロアリール基に置き換えられた化合物を原料として製造すればよい。 The compound represented by the general formula (II) can be produced according to the production method using 1,4-dibromobenzene and diphenylamine as raw materials described in Example 2 with modifications and modifications as necessary. For example, in the case of producing a compound having a phenyl group substituted with a substituent, a compound in which the desired substituent is introduced into the phenyl group of diphenylamine may be produced as a raw material instead of diphenylamine. When producing a compound having an aryl group other than a phenyl group or a heteroaryl group, a compound in which the phenyl group of diphenylamine is replaced with an aryl group or a heteroaryl group other than the phenyl group is used as a raw material instead of diphenylamine. do it.

本発明の光レドックス触媒は、光（可視光や紫外光）を照射して使用する。照射する光の波長は、光レドックス触媒の化学構造に応じて決めればよく、例えば、一般式(I)で表される化合物を含む光レドックス触媒であれば、通常、350nm〜450nmの範囲の波長であり、好ましくは、380nm〜425nmの範囲の波長であり、一般式(II)で表される化合物を含む光レドックス触媒であれば、通常、300nm〜400nmの範囲の波長であり、好ましくは、350nm〜380nmの範囲の波長である。また、照射する光は、LEDが好ましい。 The photoredox catalyst of the present invention is used by irradiating it with light (visible light or ultraviolet light). The wavelength of the light to be irradiated may be determined according to the chemical structure of the photoredox catalyst. For example, in the case of a photoredox catalyst containing a compound represented by the general formula (I), the wavelength is usually in the range of 350 nm to 450 nm. The wavelength is preferably in the range of 380 nm to 425 nm, and a photoredox catalyst containing a compound represented by the general formula (II) usually has a wavelength in the range of 300 nm to 400 nm, preferably. The wavelength is in the range of 350 nm to 380 nm. Further, the light to be irradiated is preferably an LED.

本発明の光レドックス触媒は、従来使用されているイリジウム光レドックス触媒（例えば、fac-[Ir(ppy)₃]）やルテニウム光レドックス触媒（例えば、[Ru(bpy)₃](PF₆)₂）の代替触媒になると考えられる。即ち、本発明の光レドックス触媒は、これらの金属光レドックス触媒が促進する様々な反応において触媒として使用できると考えられる。このような本発明の光レドックス触媒が使用可能な反応の具体例としては、例えば、Y. Yasu, T. Koike, M. Akita, Angew. Chem. Int. Ed., 51, 9567, (2012) に記載されている反応などを挙げることができる。 The photoredox catalyst of the present invention includes a conventionally used iridium photoredox catalyst (for example, fac- [Ir (ppy) ₃ ]) and a ruthenium photoredox catalyst (for example, [Ru (bpy) ₃ ] (PF ₆ _{) 2} ). ) Is considered to be an alternative catalyst. That is, it is considered that the photoredox catalyst of the present invention can be used as a catalyst in various reactions promoted by these metal photoredox catalysts. Specific examples of such reactions in which the photoredox catalyst of the present invention can be used include Y. Yasu, T. Koike, M. Akita, Angew. Chem. Int. Ed., 51, 9567, (2012). The reactions described in the above can be mentioned.

また、実施例に記載したように、本発明の光レドックス触媒は、芳香族アルケンのヒドロキシ−モノフルオロメチル化反応や芳香族ビニルアセテートのモノフルオロアルキル化反応の触媒として使用できる。本発明の光レドックス触媒が、一般式(II)で表される化合物を含む場合は、クロロベンゼン類の脱塩素化反応の触媒としても使用できる。 Further, as described in Examples, the photoredox catalyst of the present invention can be used as a catalyst for a hydroxy-monofluoromethylation reaction of an aromatic alkene or a monofluoroalkylation reaction of an aromatic vinyl acetate. When the photoredox catalyst of the present invention contains a compound represented by the general formula (II), it can also be used as a catalyst for the dechlorination reaction of chlorobenzenes.

以下に、実施例により本発明を更に詳細に説明するが、本発明はこれらの実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

〔実施例１〕 BDNの合成
（１）BDNの一般的合成
1,4-ジブロモナフタレン（1.14 g、4.00 mmol）、ジフェニルアミン（1.62 g、9.60 mmol）、LiHMDS（1.61 g、9.61 mmol）、Pd₂(dba)₃（36.6mg、0.0400 mmol）およびRuPhos（37.3 mg、0.0799 mmol）をいれた2つ口フラスコに、N₂雰囲気下で1,4-ジオキサン（40 mL）を加え、混合物を100℃で24時間攪拌した。室温まで冷却した後、沈殿物を濾別し、CH₂Cl₂で洗浄し、揮発物を留去した。残渣を、溶出液としてCH₂Cl₂を用いてシリカゲルパッドを通してろ過した。減圧下で濃縮した後、得られた固体をCH₂Cl₂およびMeOHを用いた再結晶により精製した。BDNを淡黄色の固体として得た(1.57 g 、3.38 mmol、85%)。 [Example 1] Synthesis of BDN (1) General synthesis of BDN
1,4-dibromonaphthalene (1.14 g, 4.00 mmol), diphenylamine (1.62 g, 9.60 mmol), LiHMDS (1.61 g, 9.61 mmol), Pd ₂ (dba) ₃ (36.6 mg, 0.0400 mmol) and RuPhos (37.3 mg) , 0.0799 mmol) was added to a two-necked flask _{under N 2} atmosphere, and the mixture was stirred at 100 ° C. for 24 hours. After cooling to room temperature, the precipitate was filtered _{off and washed with CH 2} Cl ₂ to distill off volatiles. The residue was filtered through a silica gel pad using _{CH 2} Cl _{2 as the eluate.} After concentration under reduced pressure, the resulting solid was purified by recrystallization _{with CH 2} Cl _{2 and MeOH.} BDN was obtained as a pale yellow solid (1.57 g, 3.38 mmol, 85%).

既知化合物である。¹H NMR (400 MHz, CDCl₃, rt):δ 8.00 (dd, J = 6.5 Hz, 3.3 Hz, 2H; naphthalene’s Ar), 7.34 (dd, J = 6.5 Hz, 3.3 Hz, 2H; naphthalene’s Ar), 7.32 (s, 2H; naphthalene’s Ar), 7.25-7.21 (8H; Ar), 7.07-7.05 (8H; Ar), 6.96 (t, J = 7.3 Hz, 4H; Ar).
¹³C NMR (125 MHz, CDCl₃, rt):δ 148.4, 142.3, 133.3, 129.5, 128.2, 126.9, 125.2, 122.3, 122.2.
HRMS (ESI-TOF) calcd m/z for [C34H26N2]⁺ 462.2091 found 462.2091. It is a known compound. ¹ H NMR (400 MHz, CDCl ₃ , rt): δ 8.00 (dd, J = 6.5 Hz, 3.3 Hz, 2H; naphthalene's Ar), 7.34 (dd, J = 6.5 Hz, 3.3 Hz, 2H; naphthalene's Ar), 7.32 (s, 2H; naphthalene's Ar), 7.25-7.21 (8H; Ar), 7.07-7.05 (8H; Ar), 6.96 (t, J = 7.3 Hz, 4H; Ar).
¹³ C NMR (125 MHz, CDCl ₃ , rt): δ 148.4, 142.3, 133.3, 129.5, 128.2, 126.9, 125.2, 122.3, 122.2.
HRMS (ESI-TOF) calcd m / z for [C34H26N2] ⁺ 462.2091 found 462.2091.

（２）修飾型BDNの合成
対応するジフェニルアミンを用いることで、下記の修飾型BDNを合成した。
(2) Synthesis of modified BDN The following modified BDN was synthesized by using the corresponding diphenylamine.

〔4^tBu-BDN〕
既知化合物である。¹H NMR (400 MHz, CD₂Cl₂, rt):δ 8.02 (dd, J = 6.3, 3.2 Hz, 2H), 7.34 (dd, J = 6.3, 3.2 Hz, 2H), 7.31 (s, 2H), 7.24 (d, J = 8.5 Hz, 8H), 6.97 (d, J = 8.4 Hz, 8H), 1.29 (s, 36H).
¹³C NMR (126 MHz, CD₂Cl₂, rt):δ 146.4, 144.8, 142.4, 133.4, 128.1, 126.7, 126.3, 125.3, 121.6, 34.5, 31.6. [4 ^t Bu-BDN]
It is a known compound. ^{1 1} H NMR (400 MHz, CD ₂ Cl ₂ , rt): δ 8.02 (dd, J = 6.3, 3.2 Hz, 2H), 7.34 (dd, J = 6.3, 3.2 Hz, 2H), 7.31 (s, 2H) , 7.24 (d, J = 8.5 Hz, 8H), 6.97 (d, J = 8.4 Hz, 8H), 1.29 (s, 36H).
¹³ C NMR (126 MHz, CD ₂ Cl ₂ , rt): δ 146.4, 144.8, 142.4, 133.4, 128.1, 126.7, 126.3, 125.3, 121.6, 34.5, 31.6.

〔2^tBu-BDN〕
¹H NMR (400 MHz, CD₂Cl₂, rt):δ 8.01 (dd, ³J_HH = 6.5 Hz, ⁴J_HH = 3.3 Hz, 2H; naphthalene’s Ar), 7.34 (dd, ³J_HH = 6.5 Hz, ⁴J_HH = 3.3 Hz, 2H; naphthalene’s Ar), 7.32 (s, 2H; naphthalene’s Ar), 7.28 - 7.17 (8H; Ar), 7.04 - 6.98 (8H; Ar), 6.91 (t, ³J_HH = 7.3 Hz, 2H; Ar), 1.30 (s, 18H; CH₃).
¹³C NMR (126 MHz, CD₂Cl₂, rt):δ 149.1, 146.0, 145.5, 142.3, 133.3, 129.4, 128.1, 126.8, 126.4, 125.3, 122.5, 121.4, 121.3, 34.5, 31.5.
HRMS (ESI-TOF): calcd m/z for [C₄₂H₄₂N₂]⁺ 574.3343, found 574.3345. [2 ^t Bu-BDN]
¹ H NMR (400 MHz, CD ₂ Cl ₂ , rt): δ 8.01 (dd, ³ J _HH = 6.5 Hz, ⁴ J _HH = 3.3 Hz, 2H; naphthalene's Ar), 7.34 (dd, ³ J _HH = 6.5 Hz , ⁴ J _HH = 3.3 Hz, 2H; naphthalene's Ar), 7.32 (s, 2H; naphthalene's Ar), 7.28 --7.71 (8H; Ar), 7.04 --6.98 (8H; Ar), 6.91 (t, ³ J _HH = 7.3 Hz, 2H; Ar), 1.30 (s, 18H; CH ₃ ).
¹³ C NMR (126 MHz, CD ₂ Cl ₂ , rt): δ 149.1, 146.0, 145.5, 142.3, 133.3, 129.4, 128.1, 126.8, 126.4, 125.3, 122.5, 121.4, 121.3, 34.5, 31.5.
HRMS (ESI-TOF): calcd m / z for [C ₄₂ H ₄₂ N ₂ ] ⁺ 574.3343, found 574.3345.

〔2F-BDN〕
¹H NMR (400 MHz, CD₂Cl₂, rt):δ 7.98 (dd, ³J_HH = 6.5 Hz, ⁴J_HH = 3.3 Hz, 2H; naphthalene’s Ar), 7.35 (dd, ³J_HH = 6.5 Hz, ⁴J_HH = 3.3 Hz, 2H; naphthalene’s Ar), 7.28 (s, 2H; naphthalene’s Ar), 7.21 (t, ³J_HH = 7.9 Hz, 4H; Ar), 7.09 - 7.05 (4H; Ar), 6.98 - 6.91 (10H; Ar).
¹³C NMR (126 MHz, CD₂Cl₂, rt):δ 158.3 (d, ¹J_CF = 240.9 Hz), 148.7, 144.6 (d, ⁴J_CF = 2.5 Hz), 141.8, 132.6, 129.1 (2C), 127.4, 126.5, 124.8, 124.2 (d, ³J_CF = 8.1 Hz, 2C),121.5, 121.0 (2C), 115.8 (d, ²J_CF = 22.5 Hz, 2C).
¹⁹F NMR (376 MHz, CD₂Cl₂, rt):δ -121.7 (m, 2F).
HRMS (ESI-TOF): calcd m/z for [C₃₄H₂₄F₂N₂]⁺ 498.1902, found 498.1902. [2F-BDN]
¹ H NMR (400 MHz, CD ₂ Cl ₂ , rt): δ 7.98 (dd, ³ J _HH = 6.5 Hz, ⁴ J _HH = 3.3 Hz, 2H; naphthalene's Ar), 7.35 (dd, ³ J _HH = 6.5 Hz , ⁴ J _HH = 3.3 Hz, 2H; naphthalene's Ar), 7.28 (s, 2H; naphthalene's Ar), 7.21 (t, ³ J _HH = 7.9 Hz, 4H; Ar), 7.09 --7.05 (4H; Ar), 6.98 --6.91 (10H; Ar).
¹³ C NMR (126 MHz, CD ₂ Cl ₂ , rt): δ 158.3 (d, ¹ J _CF = 240.9 Hz), 148.7, 144.6 (d, ⁴ J _CF = 2.5 Hz), 141.8, 132.6, 129.1 (2C) , 127.4, 126.5, 124.8, 124.2 (d, ³ J _CF = 8.1 Hz, 2C), 121.5, 121.0 (2C), 115.8 (d, ² J _CF = 22.5 Hz, 2C).
¹⁹ F NMR (376 MHz, CD ₂ Cl ₂ , rt): δ -121.7 (m, 2F).
HRMS (ESI-TOF): calcd m / z for [C ₃₄ H ₂₄ F ₂ N ₂ ] ⁺ 498.1902, found 498.1902.

〔実施例２〕 BDBの合成
（１）BDBの一般的合成
1,4-ジブロモベンゼン（0.472 g、2.00 mmol）、ジフェニルアミン（0.813 g、4.80 mmol）、LiHMDS（0.822 g、4.91 mmol）、Pd₂(dba)₃（19.3 mg、0.0211 mmol）およびRuPhos（18.6 mg、0.0399 mmol）をいれた2つ口フラスコに、N₂雰囲気下で1,4-ジオキサン（40 mL）を加え、混合物を100℃で24時間攪拌した。室温まで冷却した後、沈殿物を濾別し、CH₂Cl₂で洗浄し、揮発物を留去した。残渣を、溶出液としてCH₂Cl₂を用いてシリカゲルパッドを通してろ過した。減圧下で濃縮した後、得られた固体をCH₂Cl₂およびMeOHを用いた再結晶により精製した。BDBを淡黄色の固体として得た(0.772 g 、1.87 mmol、94%)。 [Example 2] Synthesis of BDB (1) General synthesis of BDB
1,4-dibromobenzene (0.472 g, 2.00 mmol), diphenylamine (0.813 g, 4.80 mmol), LiHMDS (0.822 g, 4.91 mmol), Pd ₂ (dba) ₃ (19.3 mg, 0.0211 mmol) and RuPhos (18.6 mg) , 0.0399 mmol) was added to a two-necked flask _{under N 2} atmosphere, and the mixture was stirred at 100 ° C. for 24 hours. After cooling to room temperature, the precipitate was filtered _{off and washed with CH 2} Cl ₂ to distill off volatiles. The residue was filtered through a silica gel pad using _{CH 2} Cl _{2 as the eluate.} After concentration under reduced pressure, the resulting solid was purified by recrystallization _{with CH 2} Cl _{2 and MeOH.} BDB was obtained as a pale yellow solid (0.772 g, 1.87 mmol, 94%).

既知化合物であり、スペクトルは既報（K. Kirihara, K. Okura, F. Tamakuni, E. Shirakawa, Chem. Eur. J. 2018, 24, 4519-4522.）と一致した。
¹H NMR (400 MHz, CDCl₃): δ 7.24 (dd, 3JHH = 7.3 Hz, 3JHH = 6.8 Hz, 8H; Ar), 7.10 (d, 3JHH = 7.5 Hz, 8H; Ar), 6.98 (s, 4H; benzene’ s Ar), 6.98 (t, 3JHH = 7.7 Hz, 4H; Ar). It is a known compound and its spectrum is consistent with previously reported (K. Kirihara, K. Okura, F. Tamakuni, E. Shirakawa, Chem. Eur. J. 2018, 24, 4519-4522.).
¹ H NMR (400 MHz, CDCl ₃ ): δ 7.24 (dd, 3JHH = 7.3 Hz, 3JHH = 6.8 Hz, 8H; Ar), 7.10 (d, 3JHH = 7.5 Hz, 8H; Ar), 6.98 (s, 4H) Benzene's Ar), 6.98 (t, 3JHH = 7.7 Hz, 4H; Ar).

（２）修飾型BDBの合成
対応するジフェニルアミンを用いることで、下記の修飾型BDNを合成した。
既知化合物であり、スペクトルは既報（Y. Jiang, Z. Xian, Y. Meng, G. Zhou, C. Cabanetos, J. Roncali, J.-m. Liu, J. Gao, Dyes and Pigments 2019, 162, 697-703.）と一致した。 (2) Synthesis of modified BDB The following modified BDN was synthesized by using the corresponding diphenylamine.
Known compound, spectrum previously reported (Y. Jiang, Z. Xian, Y. Meng, G. Zhou, C. Cabanetos, J. Roncali, J.-m. Liu, J. Gao, Dyes and Pigments 2019, 162 , 697-703.)

¹H NMR (400 MHz, acetone-d₆): δ 7.27 (dd, ³J_HH = 7.6 Hz, ³J_HH = 8.1 Hz, 4H; Ar), 6.97-7.14 (14H; Ar), 6.99 (s, 4H; benzene’ s Ar).
¹³C NMR (126 MHz, acetone-d₆): δ 158.74 (d, ¹J_CF = 241 Hz), 148.00, 144.15 (d, ⁴J_CF = 2.6 Hz), 143.00, 129.32, 126.10 (d, ³J_CF = 8.3 Hz), 125.07, 122.92, 122.36, 116.00 (d, ²J_CF = 22.6 Hz).
¹⁹F NMR (376 MHz, acetone-d₆): δ -121.4 (m, 2F) ¹ H NMR (400 MHz, sputtering-d ₆ ): δ 7.27 (dd, ³ J _HH = 7.6 Hz, ³ J _HH = 8.1 Hz, 4H; Ar), 6.97-7.14 (14H; Ar), 6.99 (s, 4H; benzene's Ar).
¹³ C NMR (126 MHz, acetone-d ₆ ): δ 158.74 (d, ¹ J _CF = 241 Hz), 148.00, 144.15 (d, ⁴ J _CF = 2.6 Hz), 143.00, 129.32, 126.10 (d, ³ J) _CF = 8.3 Hz), 125.07, 122.92, 122.36, 116.00 (d, ² J _CF = 22.6 Hz).
¹⁹ F NMR (376 MHz, acetone-d ₆ ): δ -121.4 (m, 2F)

〔実施例３〕ヒドロキシ−モノフルオロメチル化反応
（１）ヒドロキシ−モノフルオロメチル化の一般的方法
芳香族アルケン（0.250 mmol）、フルオロメチル化剤（0.375 mmol）、BDN（12.5 μmol）、アセトン（4.5 mL）およびH₂O（0.5 mL）を加えた20 mLシュレンクチューブを、3回凍結脱気し、水浴内で2〜3 cm離した位置から青色LEDランプ（λ= 425 nm）を照射した。室温で12〜24時間撹拌した。反応後、反応混合物を減圧下で濃縮した。シリカゲルフラッシュカラムクロマトグラフィーによる精製後に所望の生成物が得られた。必要に応じてリサイクル分取HPLCで精製した。 [Example 3] Hydroxy-monofluoromethylation reaction (1) General method of hydroxy-monofluoromethylation
A 20 mL Schlenk tube containing aromatic alkenes (0.250 mmol), fluoromethylating agent (0.375 mmol), BDN (12.5 μmol), acetone (4.5 mL) and H ₂ O (0.5 mL) was frozen and degassed three times. Then, the blue LED lamp (λ = 425 nm) was irradiated from a position 2 to 3 cm away in the water bath. The mixture was stirred at room temperature for 12 to 24 hours. After the reaction, the reaction mixture was concentrated under reduced pressure. The desired product was obtained after purification by silica gel flash column chromatography. If necessary, it was purified by recycled preparative HPLC.

（２）1-（[1,1’-ビフェニル] -4-イル）-3-フルオロプロパン-1-オール(14a)の合成
一般的方法に従い(reaction time = 12 h)、p-ビニルビフェニル13a (45.1 mg, 0.250 mmol)、化合物3(123 mg, 0.375 mmol)、BDN(5.8 mg, 12.5 μmol)、アセトン (4.5 mL)及びH₂O (0.5 mL)から化合物14aを白色固体として得た(40.3 mg, 0.175 mmol, 70%)。溶離液：ヘキサン/酢酸エチル= 4：1。 (2) Synthesis of 1-([1,1'-biphenyl] -4-yl) -3-fluoropropane-1-ol (14a)
According to common methods (reaction time = 12 h), p-vinylbiphenyl 13a (45.1 mg, 0.250 mmol), compound 3 (123 mg, 0.375 mmol), BDN (5.8 mg, 12.5 μmol), acetone (4.5 mL) and Compound 14a was obtained from H ₂ O (0.5 mL) as a white solid (40.3 mg, 0.175 mmol, 70%). Eluent: Hexane / Ethyl acetate = 4: 1.

¹H NMR (400 MHz, CDCl₃, rt): δ 7.61-7.58 (4H; Ar), 7.46-7.42 (4H; Ar), 7.37-7.33 (1H; Ar), 4.99 (m, 1 H; CH₂CHOH), 4.81-4.47 (2H; CH₂F), 2.26-2.07 (2H; CH₂CHOH), 2.02 (d, J = 2.6 Hz, 1H; CH₂CHOH).
¹³C NMR (125 MHz, CDCl₃, rt): δ 143.1, 140.9, 140.8, 128.9, 127.5 (2C), 127.2, 126.3, 81.6 (d, J = 162.3 Hz), 70.8 (d, J = 4.7 Hz), 39.7 (d, J = 19.0 Hz).
¹⁹F NMR (376 MHz, CDCl₃, r.t.): δ -222.2 (m, 1F).
HRMS (ESI-TOF) calcd m/z for [C₁₅H₁₅FO+Na]⁺ 253.0999 found 253.0999. ¹ H NMR (400 MHz, CDCl ₃ , rt): δ 7.61-7.58 (4H; Ar), 7.46-7.42 (4H; Ar), 7.37-7.33 (1H; Ar), 4.99 (m, 1 H; CH ₂₎ CHOH), 4.81-4.47 (2H; CH ₂ F), 2.26-2.07 (2H; CH ₂ CHOH), 2.02 (d, J = 2.6 Hz, 1H; CH ₂ CHOH).
¹³ C NMR (125 MHz, CDCl ₃ , rt): δ 143.1, 140.9, 140.8, 128.9, 127.5 (2C), 127.2, 126.3, 81.6 (d, J = 162.3 Hz), 70.8 (d, J = 4.7 Hz) , 39.7 (d, J = 19.0 Hz).
¹⁹ F NMR (376 MHz, CDCl ₃ , rt): δ -222.2 (m, 1F).
HRMS (ESI-TOF) calcd m / z for [C ₁₅ H ₁₅ FO + Na] ⁺ 253.0999 found 253.0999.

（３）3-フルオロ-1-フェニルプロパン-1-オール（14b）の合成
一般的方法に従い (reaction time = 12 h)、スチレン13b (26.0 mg, 0.250 mmol)、化合物3 (123 mg, 0.375 mmol)、BDN (5.8 mg, 12.5 μmol)、アセトン(4.5 mL)及びH₂O (0.5 mL)から化合物14bを無色の油として得た(20.6 mg, 0.134 mmol, 54%)。溶離液：ヘキサン/酢酸エチル= 4：1。 (3) Synthesis of 3-fluoro-1-phenylpropan-1-ol (14b)
According to common methods (reaction time = 12 h), styrene 13b (26.0 mg, 0.250 mmol), compound 3 (123 mg, 0.375 mmol), BDN (5.8 mg, 12.5 μmol), acetone (4.5 mL) and H ₂ O. Compound 14b was obtained from (0.5 mL) as a colorless oil (20.6 mg, 0.134 mmol, 54%). Eluent: Hexane / Ethyl acetate = 4: 1.

¹H NMR (400 MHz, CDCl₃, rt): δ 7.37-7.28 (5H; Ar), 4.91 (dd, J = 8.4 Hz, 5.0 Hz, 1 H; CH₂CHOH), 4.76-4.42 (2H; CH₂F), 2.22-2.02 (2H; CH₂CHOH), 2.00 (brs, 1H; CH₂CHOH).
¹³C NMR (125 MHz, CDCl₃, rt): δ 144.1, 128.8, 128.0, 125.9, 81.6 (d, J = 162.2 Hz), 71.0 (d, J = 4.5 Hz), 39.7 (d, J = 18.9 Hz).
¹⁹F NMR (376 MHz, CDCl₃, r.t.): δ -222.3 (m, 1F).
HRMS (ESI-TOF) calcd m/z for [C9H11FO+Na]⁺ 177.0686 found 177.0682. ¹ H NMR (400 MHz, CDCl ₃ , rt): δ 7.37-7.28 (5H; Ar), 4.91 (dd, J = 8.4 Hz, 5.0 Hz, 1 H; CH ₂ CHOH), 4.76-4.42 (2H; CH) ₂ F), 2.22-2.02 (2H; CH ₂ CHOH), 2.00 (brs, 1H; CH ₂ CHOH).
¹³ C NMR (125 MHz, CDCl ₃ , rt): δ 144.1, 128.8, 128.0, 125.9, 81.6 (d, J = 162.2 Hz), 71.0 (d, J = 4.5 Hz), 39.7 (d, J = 18.9 Hz) ).
¹⁹ F NMR (376 MHz, CDCl ₃ , rt): δ -222.3 (m, 1F).
HRMS (ESI-TOF) calcd m / z for [C9H11FO + Na] ⁺ 177.0686 found 177.0682.

（４）3-フルオロ-1-（p-トリル）プロパン-1-オール（14c）の合成
一般的方法に従い(reaction time = 12 h)、4-メチルスチレン13c (29.5 mg, 0.250 mmol)、化合物3 (123 mg, 0.376 mmol)、BDN(5.8 mg, 12.5 μmol)、アセトン (4.5 mL)及びH₂O (0.5 mL)から化合物14cを無色の油として得た (23.3 mg, 0.139 mmol, 55%)。溶離液：ヘキサン/酢酸エチル= 4：1。 (4) Synthesis of 3-fluoro-1- (p-tolyl) propanol-1-ol (14c)
According to common methods (reaction time = 12 h), 4-methylstyrene 13c (29.5 mg, 0.250 mmol), compound 3 (123 mg, 0.376 mmol), BDN (5.8 mg, 12.5 μmol), acetone (4.5 mL) and Compound 14c was obtained from H ₂ O (0.5 mL) as a colorless oil (23.3 mg, 0.139 mmol, 55%). Eluent: Hexane / Ethyl acetate = 4: 1.

¹H NMR (400 MHz, CDCl₃, rt): δ 7.26 (d, J = 8.0 Hz, 2H; Ar), 7.18 (d, J = 8.0 Hz, 2H; Ar), 4.87 (dd, J = 8.4 Hz, 5.0 Hz, 1 H; CH₂CHOH), 4.75-4.41 (2H; CH₂F), 2.36 (s, 3H; Me), 2.21-1.99 (2H; CH₂CHOH), 1.96 (brs, 1H; CH₂CHOH).
¹³C NMR (125 MHz, CDCl₃, rt): δ 141.1, 137.7, 129.4, 125.8, 81.6 (d, J = 162.2 Hz), 70.8 (d, J = 4.8 Hz), 39.6 (d, J = 19.0 Hz), 21.2.
¹⁹F NMR (376 MHz, CDCl₃, r.t.): δ -222.3 (m, 1F).
HRMS (ESI-TOF) calcd m/z for [C10H13FO+Na]⁺ 191.0843 found 191.0842. ^{1 1} H NMR (400 MHz, CDCl ₃ , rt): δ 7.26 (d, J = 8.0 Hz, 2H; Ar), 7.18 (d, J = 8.0 Hz, 2H; Ar), 4.87 (dd, J = 8.4 Hz) , 5.0 Hz, 1 H; CH ₂ CHOH), 4.75-4.41 (2H; CH ₂ F), 2.36 (s, 3H; Me), 2.21-1.99 (2H; CH ₂ CHOH), 1.96 (brs, 1H; CH ₂ CHOH).
¹³ C NMR (125 MHz, CDCl ₃ , rt): δ 141.1, 137.7, 129.4, 125.8, 81.6 (d, J = 162.2 Hz), 70.8 (d, J = 4.8 Hz), 39.6 (d, J = 19.0 Hz) ), 21.2.
¹⁹ F NMR (376 MHz, CDCl ₃ , rt): δ -222.3 (m, 1F).
HRMS (ESI-TOF) calcd m / z for [C10H13FO + Na] ⁺ 191.0843 found 191.0842.

（５）3-フルオロ-1-（4-フルオロフェニル）プロパン-1-オール（14d）の合成
一般的方法に従い (reaction time = 12 h)、4-フルオロスチレン13d (30.5 mg, 0.250 mmol)、化合物3 (123 mg, 0.376 mmol)、BDN (5.8 mg, 12.5 μmol)、アセトン (4.5 mL) 及び H₂O (0.5 mL) から化合物 14d を無色の油として得た (22.4 mg, 0.130 mmol, 52%)。溶離液：ヘキサン/酢酸エチル= 4：1。 (5) Synthesis of 3-fluoro-1- (4-fluorophenyl) propan-1-ol (14d)
According to common methods (reaction time = 12 h), 4-fluorostyrene 13d (30.5 mg, 0.250 mmol), compound 3 (123 mg, 0.376 mmol), BDN (5.8 mg, 12.5 μmol), acetone (4.5 mL) and Compound 14d was obtained from H ₂ O (0.5 mL) as a colorless oil (22.4 mg, 0.130 mmol, 52%). Eluent: Hexane / Ethyl acetate = 4: 1.

¹H NMR (400 MHz, CDCl₃, rt): δ 7.37-7.33 (2H; Ar), 7.08-7.02 (2H; Ar), 4.93 (m, 1 H; CH₂CHOH), 4.77-4.41 (2H; CH₂F), 2.21-1.98 (2H; CH₂CHOH), 2.00 (brs, 1H; CH₂CHOH).
¹³C NMR (125 MHz, CDCl₃, rt): δ 162.4 (d, J = 244.3 Hz), 139.8 (d, J = 9.7 Hz), 127.5 (d, J = 8.0 Hz), 115.6 (d, J = 21.3 Hz), 81.5 (d, J = 162.4 Hz), 70.4 (d, J = 4.3 Hz), 39.8 (d, J = 18.9 Hz).
¹⁹F NMR (376 MHz, CDCl₃, r.t.): δ -115.7 (m, 1F; ArF), -222.4 (m, 1F; CH₂F).
HRMS (ESI-TOF) calcd m/z for [C9H10F2O+Na]⁺ 195.0592 found 195.0588. ¹ H NMR (400 MHz, CDCl ₃ , rt): δ 7.37-7.33 (2H; Ar), 7.08-7.02 (2H; Ar), 4.93 (m, 1 H; CH ₂ CHOH), 4.77-4.41 (2H; CH ₂ F), 2.21-1.98 (2H; CH ₂ CHOH), 2.00 (brs, 1H; CH ₂ CHOH).
¹³ C NMR (125 MHz, CDCl ₃ , rt): δ 162.4 (d, J = 244.3 Hz), 139.8 (d, J = 9.7 Hz), 127.5 (d, J = 8.0 Hz), 115.6 (d, J = 21.3 Hz), 81.5 (d, J = 162.4 Hz), 70.4 (d, J = 4.3 Hz), 39.8 (d, J = 18.9 Hz).
¹⁹ F NMR (376 MHz, CDCl ₃ , rt): δ -115.7 (m, 1F; ArF), -222.4 (m, 1F; CH ₂ F).
HRMS (ESI-TOF) calcd m / z for [C9H10F2O + Na] ⁺ 195.0592 found 195.0588.

（６）1-（4-クロロフェニル）-3-フルオロプロパン-1-オール (14e)の合成
一般的方法に従い (reaction time = 12 h), 4-クロロスチレン13e (34.6 mg, 0.250 mmol)、化合物3 (123 mg, 0.375 mmol)、 BDN (5.8 mg, 12.5 μmol)、アセトン (4.5 mL) 及び H₂O (0.5 mL) から化合物 14eを無色の油として得た (24.2 mg, 0.128 mmol, 51%)。溶離液：ヘキサン/酢酸エチル= 4：1。 (6) Synthesis of 1- (4-chlorophenyl) -3-fluoropropane-1-ol (14e)
According to common methods (reaction time = 12 h), 4-chlorostyrene 13e (34.6 mg, 0.250 mmol), compound 3 (123 mg, 0.375 mmol), BDN (5.8 mg, 12.5 μmol), acetone (4.5 mL) and Compound 14e was obtained from H ₂ O (0.5 mL) as a colorless oil (24.2 mg, 0.128 mmol, 51%). Eluent: Hexane / Ethyl acetate = 4: 1.

¹H NMR (400 MHz, CDCl₃, rt): δ 7.35-7.30 (4H; Ar), 4.92 (m, 1 H; CH₂CHOH), 4.77-4.42 (2H; CH₂F), 2.19-1.99 (2H; CH₂CHOH), 2.02 (brs, 1H; CH₂CHOH).
¹³C NMR (125 MHz, CDCl₃, rt): δ 142.6, 133.6, 128.9, 127.3, 81.4 (d, J = 162.4 Hz), 70.4 (d, J = 4.2 Hz), 39.7 (d, J = 18.9 Hz).
¹⁹F NMR (376 MHz, CDCl₃, r.t.): δ -222.4 (m, 1F; CH₂F).
HRMS (ESI-TOF) calcd m/z for [C9H10ClFO+Na]⁺ 211.0296 found 211.0294. ¹ H NMR (400 MHz, CDCl ₃ , rt): δ 7.35-7.30 (4H; Ar), 4.92 (m, 1 H; CH ₂ CHOH), 4.77-4.42 (2H; CH ₂ F), 2.19-1.99 ( 2H; CH ₂ CHOH), 2.02 (brs, 1H; CH ₂ CHOH).
¹³ C NMR (125 MHz, CDCl ₃ , rt): δ 142.6, 133.6, 128.9, 127.3, 81.4 (d, J = 162.4 Hz), 70.4 (d, J = 4.2 Hz), 39.7 (d, J = 18.9 Hz) ).
¹⁹ F NMR (376 MHz, CDCl ₃ , rt): δ -222.4 (m, 1F; CH ₂ F).
HRMS (ESI-TOF) calcd m / z for [C9H10ClFO + Na] ⁺ 211.0296 found 211.0294.

（７）1-（4-ブロモフェニル）-3-フルオロプロパン-1-オール (14f)の合成
一般的方法に従い (reaction time = 12 h)、4-ブロモスチレン13f (45.8 mg, 0.250 mmol)、化合物3(123 mg, 0.377 mmol)、BDN (5.8 mg, 12.5 μmol)、アセトン (4.5 mL) 及び H₂O (0.5 mL) から化合物 14fを無色の油として得た (32.3 mg, 0.139 mmol, 55%)。溶離液：ヘキサン/酢酸エチル= 4：1。 (7) Synthesis of 1- (4-Bromophenyl) -3-fluoropropane-1-ol (14f)
According to common methods (reaction time = 12 h), 4-bromostyrene 13f (45.8 mg, 0.250 mmol), compound 3 (123 mg, 0.377 mmol), BDN (5.8 mg, 12.5 μmol), acetone (4.5 mL) and Compound 14f was obtained from H ₂ O (0.5 mL) as a colorless oil (32.3 mg, 0.139 mmol, 55%). Eluent: Hexane / Ethyl acetate = 4: 1.

¹H NMR (400 MHz, CDCl₃, rt): δ 7.49 (d, J = 8.4 Hz, 2H; Ar), 7.26 (d, J = 8.4 Hz, 2H; Ar), 4.91 (m, 1 H; CH₂CHOH), 4.78-4.42 (2H; CH₂F), 2.18-1.97 (2H; CH₂CHOH), 2.03 (brs, 1H; CH₂CHOH).
¹³C NMR (125 MHz, CDCl₃, rt): δ 143.1, 131.8, 127.6, 121.7, 81.4 (d, J = 162.5 Hz), 70.5 (d, J = 4.2 Hz), 39.7 (d, J = 18.8 Hz).
¹⁹F NMR (376 MHz, CDCl₃, r.t.): δ -222.4 (m, 1F; CH₂F).
HRMS (ESI-TOF) calcd m/z for [C9H10BrFO+Na]⁺ 254.9791 found 254.9791. ¹ H NMR (400 MHz, CDCl ₃ , rt): δ 7.49 (d, J = 8.4 Hz, 2H; Ar), 7.26 (d, J = 8.4 Hz, 2H; Ar), 4.91 (m, 1 H; CH ₂ CHOH), 4.78-4.42 (2H; CH ₂ F), 2.18-1.97 (2H; CH ₂ CHOH), 2.03 (brs, 1H; CH ₂ CHOH).
¹³ C NMR (125 MHz, CDCl ₃ , rt): δ 143.1, 131.8, 127.6, 121.7, 81.4 (d, J = 162.5 Hz), 70.5 (d, J = 4.2 Hz), 39.7 (d, J = 18.8 Hz) ).
¹⁹ F NMR (376 MHz, CDCl ₃ , rt): δ -222.4 (m, 1F; CH ₂ F).
HRMS (ESI-TOF) calcd m / z for [C9H10BrFO + Na] ⁺ 254.9791 found 254.9791.

（８）3-フルオロ-1-（4-メトキシフェニル）プロパン-1-オール(14g)の合成
一般的方法に従い (reaction time = 12 h)、4-メトキシスチレン13g (33.5 mg, 0.250 mmol)、化合物3 (123 mg, 0.376 mmol)、BDN (5.8 mg, 12.5 μmol)、アセトン (4.5 mL) 及び H₂O (0.5 mL) から化合物 14gを無色の油として得た (31.1 mg, 0.169 mmol, 68%)。溶離液：ヘキサン/酢酸エチル= 4：1。 (8) Synthesis of 3-fluoro-1- (4-methoxyphenyl) propan-1-ol (14 g)
According to common methods (reaction time = 12 h), 4-methoxystyrene 13 g (33.5 mg, 0.250 mmol), compound 3 (123 mg, 0.376 mmol), BDN (5.8 mg, 12.5 μmol), acetone (4.5 mL) and 14 g of compound was obtained from H ₂ O (0.5 mL) as colorless oil (31.1 mg, 0.169 mmol, 68%). Eluent: Hexane / Ethyl acetate = 4: 1.

¹H NMR (400 MHz, CDCl₃, rt): δ 7.30 (d, J = 8.7 Hz, 2H; Ar), 6.91 (d, J = 8.7 Hz, 2H; Ar), 4.88 (m, 1 H; CH₂CHOH), 4.75-4.41 (2H; CH₂F), 3.81 (s, 3H; OMe), 2.24-1.98 (2H; CH₂CHOH), 1.90 (brs, 1H; CH₂CHOH).
¹³C NMR (125 MHz, CDCl₃, rt): δ 159.4, 136.2, 127.2, 114.1, 81.6 (d, J = 162.2 Hz), 70.6 (d, J = 4.8 Hz), 55.4, 39.6 (d, J = 19.0 Hz).
¹⁹F NMR (376 MHz, CDCl₃, r.t.): δ -222.4 (m, 1F; CH₂F).
HRMS (ESI-TOF) calcd m/z for [C10H13FO2+Na]⁺ 207.0792 found 207.0792. ^{1 1} H NMR (400 MHz, CDCl ₃ , rt): δ 7.30 (d, J = 8.7 Hz, 2H; Ar), 6.91 (d, J = 8.7 Hz, 2H; Ar), 4.88 (m, 1 H; CH ₂ CHOH), 4.75-4.41 (2H; CH ₂ F), 3.81 (s, 3H; OMe), 2.24-1.98 (2H; CH ₂ CHOH), 1.90 (brs, 1H; CH ₂ CHOH).
¹³ C NMR (125 MHz, CDCl ₃ , rt): δ 159.4, 136.2, 127.2, 114.1, 81.6 (d, J = 162.2 Hz), 70.6 (d, J = 4.8 Hz), 55.4, 39.6 (d, J = 19.0 Hz).
¹⁹ F NMR (376 MHz, CDCl ₃ , rt): δ -222.4 (m, 1F; CH ₂ F).
HRMS (ESI-TOF) calcd m / z for [C10H13FO2 + Na] ⁺ 207.0792 found 207.0792.

（９）4-（3-フルオロ-1-ヒドロキシプロピル）フェニルアセテート (14h)の合成
一般的方法に従い (reaction time = 12 h), 4-アセトキシスチレン13h (40.5 mg, 0.250 mmol)、化合物3 (123 mg, 0.375 mmol)、BDN (5.8 mg, 12.5 μmol)、アセトン (4.5 mL) 及び H₂O (0.5 mL) から化合物 14hを無色の油として得た (31.5 mg, 0.148 mmol, 59%)。溶離液：ヘキサン/酢酸エチル= 4：1。 (9) Synthesis of 4- (3-fluoro-1-hydroxypropyl) phenylacetate (14h)
According to common methods (reaction time = 12 h), 4-acetoxystyrene 13 h (40.5 mg, 0.250 mmol), compound 3 (123 mg, 0.375 mmol), BDN (5.8 mg, 12.5 μmol), acetone (4.5 mL) and Compound 14h was obtained from H ₂ O (0.5 mL) as a colorless oil (31.5 mg, 0.148 mmol, 59%). Eluent: Hexane / Ethyl acetate = 4: 1.

¹H NMR (400 MHz, CDCl₃, rt): δ 7.39 (d, J = 8.5 Hz, 2H; Ar), 7.09 (d, J = 8.5 Hz, 2H; Ar), 4.94 (dd, J = 8.3 Hz, 4.8 Hz, 1 H; CH₂CHOH), 4.78-4.43 (2H; CH₂F), 2.30 (s, 3H; OAc), 2.21-2.01 (2H; CH₂CHOH), 2.00 (brs, 1H; CH₂CHOH).
¹³C NMR (125 MHz, CDCl₃, rt): δ 169.7, 150.2, 141.7, 127.0, 121.8, 81.5 (d, J = 162.4 Hz), 70.4 (d, J = 3.8 Hz), 39.6 (d, J = 19.0 Hz), 21.2.
¹⁹F NMR (376 MHz, CDCl₃, r.t.): δ -222.4 (m, 1F; CH₂F).
HRMS (ESI-TOF) calcd m/z for [C11H13FO3+Na]⁺ 235.0741 found 235.0739. ^{1 1} H NMR (400 MHz, CDCl ₃ , rt): δ 7.39 (d, J = 8.5 Hz, 2H; Ar), 7.09 (d, J = 8.5 Hz, 2H; Ar), 4.94 (dd, J = 8.3 Hz , 4.8 Hz, 1 H; CH ₂ CHOH), 4.78-4.43 (2H; CH ₂ F), 2.30 (s, 3H; OAc), 2.21-2.01 (2H; CH ₂ CHOH), 2.00 (brs, 1H; CH ₂ CHOH).
¹³ C NMR (125 MHz, CDCl ₃ , rt): δ 169.7, 150.2, 141.7, 127.0, 121.8, 81.5 (d, J = 162.4 Hz), 70.4 (d, J = 3.8 Hz), 39.6 (d, J = 19.0 Hz), 21.2.
¹⁹ F NMR (376 MHz, CDCl ₃ , rt): δ -222.4 (m, 1F; CH ₂ F).
HRMS (ESI-TOF) calcd m / z for [C11H13FO3 + Na] ⁺ 235.0741 found 235.0739.

（１０）3-フルオロ-1-（4-（トリメチルシリル）フェニル）プロパン-1-オール(14i)の合成
一般的方法に従い (reaction time = 12 h)、トリメチル（4-ビニルフェニル）シラン13i (44.1 mg, 0.250 mmol)、化合物3 (123 mg, 0.377 mmol)、 BDN (5.8 mg, 12.5 μmol)、アセトン (4.5 mL) 及び H₂O (0.5 mL) から化合物14iを無色の油として得た (30.9 mg, 0.137 mmol, 55%)。溶離液：ヘキサン/酢酸エチル= 4：1。 (10) Synthesis of 3-fluoro-1- (4- (trimethylsilyl) phenyl) propanol-1-ol (14i)
According to common methods (reaction time = 12 h), trimethyl (4-vinylphenyl) silane 13i (44.1 mg, 0.250 mmol), compound 3 (123 mg, 0.377 mmol), BDN (5.8 mg, 12.5 μmol), acetone ( Compound 14i was obtained as a colorless oil from 4.5 mL) and H ₂ O (0.5 mL) (30.9 mg, 0.137 mmol, 55%). Eluent: Hexane / Ethyl acetate = 4: 1.

¹H NMR (400 MHz, CDCl₃, rt): δ 7.54 (d, J = 7.9 Hz, 2H; Ar), 7.36 (d, J = 7.9 Hz, 2H; Ar), 4.91 (dd, J = 8.2 Hz, 5.0 Hz, 1 H; CH₂CHOH), 4.78-4.43 (2H; CH₂F), 2.22-2.02 (2H; CH₂CHOH), 1.98 (brs, 1H; CH₂CHOH), 0.28 (s, 9H; SiMe3).
¹³C NMR (125 MHz, CDCl₃, rt): δ 144.6, 140.3, 133.8, 125.3, 81.6 (d, J = 162.3 Hz), 70.9 (d, J = 4.5 Hz), 39.6 (d, J = 19.0 Hz), -1.00.
¹⁹F NMR (376 MHz, CDCl₃, r.t.): δ -222.3 (m, 1F; CH₂F).
HRMS (ESI-TOF) calcd m/z for [C12H19FOSi+Na]⁺ 249.1081 found 249.1080. ^{1 1} H NMR (400 MHz, CDCl ₃ , rt): δ 7.54 (d, J = 7.9 Hz, 2H; Ar), 7.36 (d, J = 7.9 Hz, 2H; Ar), 4.91 (dd, J = 8.2 Hz) , 5.0 Hz, 1 H; CH ₂ CHOH), 4.78-4.43 (2H; CH ₂ F), 2.22-2.02 (2H; CH ₂ CHOH), 1.98 (brs, 1H; CH ₂ CHOH), 0.28 (s, 9H) SiMe3).
¹³ C NMR (125 MHz, CDCl ₃ , rt): δ 144.6, 140.3, 133.8, 125.3, 81.6 (d, J = 162.3 Hz), 70.9 (d, J = 4.5 Hz), 39.6 (d, J = 19.0 Hz) ), -1.00.
¹⁹ F NMR (376 MHz, CDCl ₃ , rt): δ -222.3 (m, 1F; CH ₂ F).
HRMS (ESI-TOF) calcd m / z for [C12H19FOSi + Na] ⁺ 249.1081 found 249.1080.

（１１）2-（フルオロメチル）-2,3-ジヒドロ-1H-インデン-1-オール(14j)の合成
一般的方法に従い (reaction time = 24 h)、インデン13j (29.0 mg, 0.250 mmol), 化合物3 (123 mg, 0.377 mmol)、BDN (9.3 mg, 20.1 μmol)、アセトン (4.5 mL) 及び H₂O (0.5 mL) から化合物 14jを無色の油として得た(11.0 mg, 0.0662 mmol, 27%, diastereomeric ratio = 1.1:1)。溶離液：ヘキサン/酢酸エチル= 4：1。 (11) Synthesis of 2- (fluoromethyl) -2,3-dihydro-1H-indene-1-ol (14j)
According to common methods (reaction time = 24 h), Inden 13j (29.0 mg, 0.250 mmol), Compound 3 (123 mg, 0.377 mmol), BDN (9.3 mg, 20.1 μmol), Acetone (4.5 mL) and H ₂ O. Compound 14j was obtained from (0.5 mL) as a colorless oil (11.0 mg, 0.0662 mmol, 27%, diastereomeric ratio = 1.1: 1). Eluent: Hexane / Ethyl acetate = 4: 1.

¹H NMR (400 MHz, CDCl₃, rt): δ 7.44-7.22 (2H; Ar of major and minor isomers), 5.26 (d, J = 6.0 Hz, 1H; CHCHOH of minor isomer), 5.26 (d, J = 6.4 Hz, 1H; CHCHOH of major isomer), 4.92-4.53 (2H; CH₂F of major and minor isomers), 3.16-2.57 (3H; CHCHOH, ArCH₂CH of major and minor isomers), 1.78 (brs, 1H; CHCHOH of major and minor isomers).
¹³C NMR (125 MHz, CDCl₃, rt): δ 84.6 (d, J = 166.8 Hz), 83.7 (d, J = 163.2 Hz), 77.8 (d, J = 6.0 Hz), 75.8 (d, J = 4.8 Hz), 50.8 (d, J = 18.1 Hz), 44.4 (d, J = 18.3 Hz), 32.5 (d, J = 8.3 Hz), 32.1 (d, J = 6.1 Hz).
Aromatic signals of major and minor diastereomers were overlapped around (144.1, 143.9, 142.4, 141.1, 129.1, 128.7, 127.2, 125.2, 125.1, 125.0, 124.3).
¹⁹F NMR (376 MHz, CDCl₃, r.t.): δ -222.9 (m, 1F; CH₂F of minor isomer), -223.3 (m, 1F; CH₂F of major isomer).
HRMS (ESI-TOF) calcd m/z for [C10H11FO+Na]⁺ 189.0686 found 189.0688. ¹ H NMR (400 MHz, CDCl ₃ , rt): δ 7.44-7.22 (2H; Ar of major and minor isomers), 5.26 (d, J = 6.0 Hz, 1H; CHCHOH of minor isomers), 5.26 (d, J = 6.4 Hz, 1H; CHCHOH of major _{isomers), 4.92-4.53 (2H; CH 2} F of major and minor isomers), 3.16-2.57 (3H; CHCHOH, ArCH ₂ CH of major and minor isomers), 1.78 (brs, 1H; CHCHOH of major and minor isomers).
¹³ C NMR (125 MHz, CDCl ₃ , rt): δ 84.6 (d, J = 166.8 Hz), 83.7 (d, J = 163.2 Hz), 77.8 (d, J = 6.0 Hz), 75.8 (d, J = 4.8 Hz), 50.8 (d, J = 18.1 Hz), 44.4 (d, J = 18.3 Hz), 32.5 (d, J = 8.3 Hz), 32.1 (d, J = 6.1 Hz).
Aromatic signals of major and minor diastereomers were overlapped around (144.1, 143.9, 142.4, 141.1, 129.1, 128.7, 127.2, 125.2, 125.1, 125.0, 124.3).
¹⁹ F NMR (376 MHz, CDCl ₃ , rt): δ -222.9 (m, 1F; CH ₂ F of minor isomer), -223.3 (m, 1F; CH ₂ F of major isomer).
HRMS (ESI-TOF) calcd m / z for [C10H11FO + Na] ⁺ 189.0686 found 189.0688.

（１２）3-フルオロ-1-（m-トリル）プロパン-1-オール(14k)の合成
一般的方法に従い (reaction time = 12 h)、3-メチルスチレン13k (29.5 mg, 0.250 mmol)、化合物3 (123 mg, 0.376 mmol)、BDN (5.8 mg, 12.5 μmol)、アセトン (4.5 mL) 及び H₂O (0.5 mL) から化合物 14kを無色の油として得た (19.7mg, 0.117 mmol, 47%)。溶離液：ヘキサン/酢酸エチル= 4：1。 (12) Synthesis of 3-fluoro-1- (m-tolyl) propanol-1-ol (14k)
According to common methods (reaction time = 12 h), 3-methylstyrene 13k (29.5 mg, 0.250 mmol), compound 3 (123 mg, 0.376 mmol), BDN (5.8 mg, 12.5 μmol), acetone (4.5 mL) and Compound 14k was obtained from H ₂ O (0.5 mL) as a colorless oil (19.7 mg, 0.117 mmol, 47%). Eluent: Hexane / Ethyl acetate = 4: 1.

¹H NMR (400 MHz, CDCl₃, rt): δ 7.28-7.11 (4H; Ar), 4.89 (m, 1 H; CH₂CHOH), 4.77-4.43 (2H; CH₂F), 2.37 (s, 3H; Me), 2.23-2.02 (2H; CH₂CHOH), 1.96 (brd, J = 2.7 Hz, 1H; CH₂CHOH).
¹³C NMR (125 MHz, CDCl₃, rt): δ 144.1, 138.5, 128.70, 128.67, 126.6, 122.9, 81.6 (d, J = 162.3 Hz), 71.0 (d, J = 4.4 Hz), 39.7 (d, J = 19.0 Hz), 21.6.
¹⁹F NMR (376 MHz, CDCl₃, r.t.): δ -222.3 (m, 1F).
HRMS (ESI-TOF) calcd m/z for [C10H13FO+Na]⁺ 191.0843 found 191.0848. ^{1 1} H NMR (400 MHz, CDCl ₃ , rt): δ 7.28-7.11 (4H; Ar), 4.89 (m, 1 H; CH ₂ CHOH), 4.77-4.43 (2H; CH ₂ F), 2.37 (s, 3H; Me), 2.23-2.02 (2H; CH ₂ CHOH), 1.96 (brd, J = 2.7 Hz, 1H; CH ₂ CHOH).
¹³ C NMR (125 MHz, CDCl ₃ , rt): δ 144.1, 138.5, 128.70, 128.67, 126.6, 122.9, 81.6 (d, J = 162.3 Hz), 71.0 (d, J = 4.4 Hz), 39.7 (d, J = 19.0 Hz), 21.6.
¹⁹ F NMR (376 MHz, CDCl ₃ , rt): δ -222.3 (m, 1F).
HRMS (ESI-TOF) calcd m / z for [C10H13FO + Na] ⁺ 191.0843 found 191.0848.

（１３）3-フルオロ-1-（o-トリル）プロパン-1-オール(14l)の合成
一般的方法に従い (reaction time = 12 h)、2-メチルスチレン13l (29.5 mg, 0.250 mmol)、化合物3(123 mg, 0.376 mmol)、BDN (5.8 mg, 12.5 μmol)、アセトン (4.5 mL) 及び H₂O (0.5 mL) から化合物 14lを無色の油として得た (21.6 mg, 0.128 mmol, 51%)。溶離液：ヘキサン/酢酸エチル= 4：1。 (13) Synthesis of 3-fluoro-1- (o-tolyl) propanol-1-ol (14l)
According to common methods (reaction time = 12 h), 2-methylstyrene 13 l (29.5 mg, 0.250 mmol), compound 3 (123 mg, 0.376 mmol), BDN (5.8 mg, 12.5 μmol), acetone (4.5 mL) and From H ₂ O (0.5 mL), 14 l of compound was obtained as a colorless oil (21.6 mg, 0.128 mmol, 51%). Eluent: Hexane / Ethyl acetate = 4: 1.

¹H NMR (400 MHz, CDCl₃, rt): δ 7.49 (d, J = 7.4 Hz, 2H; Ar), 7.27-7.15 (3H; Ar), 5.17 (dd, J = 8.4 Hz, 5.5 Hz, 1 H; CH₂CHOH), 4.82-4.46 (2H; CH₂F), 2.35 (s, 3H; Me), 2.16-1.96 (2H; CH₂CHOH), 2.00 (brs, 1H; CH₂CHOH).
¹³C NMR (125 MHz, CDCl₃, rt): δ 142.2, 134.5, 130.6, 127.6, 126.6, 125.1, 81.7 (d, J = 162.2 Hz), 67.2 (d, J = 4.3 Hz), 38.7 (d, J = 19.1 Hz), 19.0.
¹⁹F NMR (376 MHz, CDCl₃, r.t.): δ -222.0 (m, 1F).
HRMS (ESI-TOF) calcd m/z for [C10H13FO+Na]⁺ 191.0843 found 191.0840. ^{1 1} H NMR (400 MHz, CDCl ₃ , rt): δ 7.49 (d, J = 7.4 Hz, 2H; Ar), 7.27-7.15 (3H; Ar), 5.17 (dd, J = 8.4 Hz, 5.5 Hz, 1 H; CH ₂ CHOH), 4.82-4.46 (2H; CH ₂ F), 2.35 (s, 3H; Me), 2.16-1.96 (2H; CH ₂ CHOH), 2.00 (brs, 1H; CH ₂ CHOH).
¹³ C NMR (125 MHz, CDCl ₃ , rt): δ 142.2, 134.5, 130.6, 127.6, 126.6, 125.1, 81.7 (d, J = 162.2 Hz), 67.2 (d, J = 4.3 Hz), 38.7 (d, J = 19.1 Hz), 19.0.
¹⁹ F NMR (376 MHz, CDCl ₃ , rt): δ -222.0 (m, 1F).
HRMS (ESI-TOF) calcd m / z for [C10H13FO + Na] ⁺ 191.0843 found 191.0840.

（１４）3-フルオロ-1,1-ジフェニルプロパン-1-オール(16a)の合成
一般的方法に従い (reaction time = 12 h)、1,1-ジフェニルエチレン15a (45.1 mg, 0.250 mmol)、化合物3 (123 mg, 0.375 mmol)、BDN (5.8 mg, 12.5 μmol)、アセトン (4.5 mL) 及び H₂O (0.5 mL) から化合物 16aを白い油性固体として得た (48.2 mg, 0.209 mmol, 84%)。溶離液：ヘキサン/酢酸エチル= 10:1. (14) Synthesis of 3-fluoro-1,1-diphenylpropan-1-ol (16a)
According to common methods (reaction time = 12 h), 1,1-diphenylethylene 15a (45.1 mg, 0.250 mmol), compound 3 (123 mg, 0.375 mmol), BDN (5.8 mg, 12.5 μmol), acetone (4.5 mL) ) And H ₂ O (0.5 mL) gave compound 16a as a white oily solid (48.2 mg, 0.209 mmol, 84%). Eluent: Hexane / Ethyl Acetate = 10: 1.

¹H NMR (400 MHz, CDCl₃, rt): δ 7.43-7.41 (4H; Ar), 7.35-7.31 (4H; Ar), 7.26-7.23 (2H; Ar), 4.56 (dt, J = 47.1 Hz, 6.4 Hz, 2H; CH₂CH₂F), 2.77 (dt, J = 21.6 Hz, 6.4 Hz, 2H; CH₂CH₂F), 2.59 (brs, 1H; OH).
¹³C NMR (125 MHz, CDCl₃, rt): δ 146.3, 128.5, 127.3, 125.9, 82.1 (d, J = 160.0 Hz), 77.5 (overlapped by CDCl₃), 41.7 (d, J = 17.9 Hz).
¹⁹F NMR (376 MHz, CDCl₃, r.t.): δ -221.3 (m, 1F; CH₂F).
HRMS (ESI-TOF) calcd m/z for [C15H15FO+Na]⁺ 253.0999 found 253.1004. ^{1 1} H NMR (400 MHz, CDCl ₃ , rt): δ 7.43-7.41 (4H; Ar), 7.35-7.31 (4H; Ar), 7.26-7.23 (2H; Ar), 4.56 (dt, J = 47.1 Hz, 6.4 Hz, 2H; CH ₂ CH ₂ F), 2.77 (dt, J = 21.6 Hz, 6.4 Hz, 2H; CH ₂ CH ₂ F), 2.59 (brs, 1H; OH).
¹³ C NMR (125 MHz, CDCl ₃ , rt): δ 146.3, 128.5, 127.3, 125.9, 82.1 (d, J = 160.0 Hz), 77.5 (overlapped by CDCl ₃ ), 41.7 (d, J = 17.9 Hz).
¹⁹ F NMR (376 MHz, CDCl ₃ , rt): δ -221.3 (m, 1F; CH ₂ F).
HRMS (ESI-TOF) calcd m / z for [C15H15FO + Na] ⁺ 253.0999 found 253.1004.

（１５）3-フルオロ-1-フェニル-1-（p-トリル）プロパン-1-オール(16b)の合成
一般的方法に従い (reaction time = 12 h)、1-メチル-4-（1-フェニルビニル）ベンゼン15b (48.6 mg, 0.250 mmol)、化合物3 (123 mg, 0.375 mmol)、BDN (5.8 mg, 12.5 μmol)、アセトン (4.5 mL) 及び H₂O (0.5 mL)から化合物 16bを無色の油として得た (48.2 mg, 0.197 mmol, 79%)。溶離液：ヘキサン/酢酸エチル= 10:1。 (15) Synthesis of 3-fluoro-1-phenyl-1- (p-tolyl) propanol-1-ol (16b)
According to the general method (reaction time = 12 h), 1-methyl-4- (1-phenylvinyl) benzene 15b (48.6 mg, 0.250 mmol), compound 3 (123 mg, 0.375 mmol), BDN (5.8 mg, 12.5 mmol). Compound 16b was obtained as a colorless oil from μmol), acetone (4.5 mL) and H ₂ O (0.5 mL) (48.2 mg, 0.197 mmol, 79%). Eluent: Hexane / Ethyl acetate = 10: 1.

¹H NMR (400 MHz, CDCl₃, rt): δ 7.42-7.40 (2H; Ar), 7.33-7.28 (4H; Ar), 7.24 (m, 1H; Ar), 7.14 (d, J = 8.0 Hz, 2H; Ar), 4.56 (apparent dtd, J = 47.1 Hz, 6.5 Hz, 1.2 Hz, 2H; CH₂CH₂F), 2.74 (apparent dt, J = 21.4 Hz, 6.4 Hz, 2H; CH₂CH₂F), 2.53 (d, J = 6.0 Hz, 1H; OH), 2.32 (s, 3H, Me).
¹³C NMR (125 MHz, CDCl₃, rt): δ 146.4, 143.4, 137.0, 129.2, 128.4, 127.2, 125.89, 125.87, 82.2 (d, J = 159.9 Hz), 77.3 (d, J = 6.6 Hz), 41.7 (d, J = 18.1 Hz), 21.1.
¹⁹F NMR (376 MHz, CDCl₃, r.t.): δ -221.3 (m, 1F; CH₂F).
HRMS (ESI-TOF) calcd m/z for [C16H17FO+Na]⁺ 267.1156 found 267.1154. ¹ H NMR (400 MHz, CDCl ₃ , rt): δ 7.42-7.40 (2H; Ar), 7.33-7.28 (4H; Ar), 7.24 (m, 1H; Ar), 7.14 (d, J = 8.0 Hz, 2H; Ar), 4.56 (apparent dtd, J = 47.1 Hz, 6.5 Hz, 1.2 Hz, 2H; CH ₂ CH ₂ F), 2.74 (apparent dt, J = 21.4 Hz, 6.4 Hz, 2H; CH ₂ CH ₂ F ), 2.53 (d, J = 6.0 Hz, 1H; OH), 2.32 (s, 3H, Me).
¹³ C NMR (125 MHz, CDCl ₃ , rt): δ 146.4, 143.4, 137.0, 129.2, 128.4, 127.2, 125.89, 125.87, 82.2 (d, J = 159.9 Hz), 77.3 (d, J = 6.6 Hz), 41.7 (d, J = 18.1 Hz), 21.1.
¹⁹ F NMR (376 MHz, CDCl ₃ , rt): δ -221.3 (m, 1F; CH ₂ F).
HRMS (ESI-TOF) calcd m / z for [C16H17FO + Na] ⁺ 267.1156 found 267.1154.

（１６）3-フルオロ-1-（4-フルオロフェニル）-1-フェニルプロパン-1-オール(16c)の合成
一般的方法に従い (reaction time = 12 h)、1-フルオロ-4-（1-フェニルビニル）ベンゼン15c (49.6 mg, 0.250 mmol)、化合物3 (123 mg, 0.376 mmol)、BDN (5.8 mg, 12.5 μmol)、アセトン (4.5 mL) 及び H₂O (0.5 mL)から化合物 16cを無色の油として得た (48.1 mg, 0.194 mmol, 77%)。溶離液：ヘキサン/酢酸エチル= 10:1。 (16) Synthesis of 3-fluoro-1- (4-fluorophenyl) -1-phenylpropan-1-ol (16c)
According to the general method (reaction time = 12 h), 1-fluoro-4- (1-phenylvinyl) benzene 15c (49.6 mg, 0.250 mmol), compound 3 (123 mg, 0.376 mmol), BDN (5.8 mg, 12.5). Compound 16c was obtained as a colorless oil from μmol), acetone (4.5 mL) and H ₂ O (0.5 mL) (48.1 mg, 0.194 mmol, 77%). Eluent: Hexane / Ethyl acetate = 10: 1.

¹H NMR (400 MHz, CDCl₃, rt): δ 7.41-7.32 (6H; Ar), 7.26 (m, 1H; Ar), 7.04-6.98 (2H; Ar), 4.56 (apparent dt, J = 47.0 Hz, 6.3 Hz, 2H; CH₂CH₂F), 2.74 (apparent dt, J = 22.2 Hz, 6.3 Hz, 2H; CH₂CH₂F), 2.62 (d, J = 6.8 Hz, 1H; OH).
¹³C NMR (125 MHz, CDCl₃, rt): δ 161.9 (d, J = 244.8 Hz), 146.0, 142.1 (d, J = 2.9 Hz), 128.6, 127.8 (d, J = 8.2 Hz), 127.5, 125.9, 115.2 (d, J = 21.1 Hz), 82.0 (d, J = 160.3 Hz), 77.2 (d, J = 6.0 Hz), 41.8 (d, J = 17.9 Hz).
¹⁹F NMR (376 MHz, CDCl₃, r.t.): δ -116.7 (m, 1F; ArF), -222.2 (m, 1F; CH₂F).
HRMS (ESI-TOF) calcd m/z for [C15H14F2O+Na]⁺ 271.0905 found 271.0905. ^{1 1} H NMR (400 MHz, CDCl ₃ , rt): δ 7.41-7.32 (6H; Ar), 7.26 (m, 1H; Ar), 7.04-6.98 (2H; Ar), 4.56 (apparent dt, J = 47.0 Hz) , 6.3 Hz, 2H; CH ₂ CH ₂ F), 2.74 (apparent dt, J = 22.2 Hz, 6.3 Hz, 2H; CH ₂ CH ₂ F), 2.62 (d, J = 6.8 Hz, 1H; OH).
¹³ C NMR (125 MHz, CDCl ₃ , rt): δ 161.9 (d, J = 244.8 Hz), 146.0, 142.1 (d, J = 2.9 Hz), 128.6, 127.8 (d, J = 8.2 Hz), 127.5, 125.9, 115.2 (d, J = 21.1 Hz), 82.0 (d, J = 160.3 Hz), 77.2 (d, J = 6.0 Hz), 41.8 (d, J = 17.9 Hz).
¹⁹ F NMR (376 MHz, CDCl ₃ , rt): δ -116.7 (m, 1F; ArF), -222.2 (m, 1F; CH ₂ F).
HRMS (ESI-TOF) calcd m / z for [C15H14F2O + Na] ⁺ 271.0905 found 271.0905.

（１７）1-（4-クロロフェニル）-3-フルオロ-1-フェニルプロパン-1-オール(16d)の合成
一般的方法に従い (reaction time = 12 h)、1-クロロ-4-（1-フェニルビニル）ベンゼン15d (53.7 mg, 0.250 mmol)、化合物3 (123 mg, 0.376 mmol)、BDN (5.8 mg, 12.5 μmol)、アセトン (4.5 mL) 及び H₂O (0.5 mL)から化合物 16dを無色の油として得た (41.7 mg, 0.158 mmol, 63%)。溶離液：ヘキサン/酢酸エチル= 10:1。 (17) Synthesis of 1- (4-chlorophenyl) -3-fluoro-1-phenylpropan-1-ol (16d)
According to the general method (reaction time = 12 h), 1-chloro-4- (1-phenylvinyl) benzene 15d (53.7 mg, 0.250 mmol), compound 3 (123 mg, 0.376 mmol), BDN (5.8 mg, 12.5). Compound 16d was obtained as a colorless oil from μmol), acetone (4.5 mL) and H ₂ O (0.5 mL) (41.7 mg, 0.158 mmol, 63%). Eluent: Hexane / Ethyl acetate = 10: 1.

¹H NMR (400 MHz, CDCl₃, rt): δ 7.41-7.24 (9H; Ar), 4.56 (apparent dtd, J = 47.0 Hz, 6.2 Hz, 1.7 Hz, 2H; CH₂CH₂F), 2.73 (apparent dt, J = 22.3 Hz, 6.2 Hz, 2H; CH₂CH₂F), 2.64 (d, J = 7.0 Hz, 1H; OH).
¹³C NMR (125 MHz, CDCl₃, rt): δ 145.8, 144.8, 133.1, 128.61, 128.56, 127.6, 127.5, 125.8, 82.0 (d, J = 160.1 Hz), 77.2 (d, J = 5.6 Hz), 41.6 (d, J = 18.1 Hz).
¹⁹F NMR (376 MHz, CDCl₃, r.t.): δ -221.2 (m, 1F; CH₂F).
HRMS (ESI-TOF) calcd m/z for [C15H14FOCl+Na]⁺ 287.0609 found 287.0610. ¹ H NMR (400 MHz, CDCl ₃ , rt): δ 7.41-7.24 (9H; Ar), 4.56 (apparent dtd, J = 47.0 Hz, 6.2 Hz, 1.7 Hz, 2H; CH ₂ CH ₂ F), 2.73 ( apparent dt, J = 22.3 Hz, 6.2 Hz, 2H; CH ₂ CH ₂ F), 2.64 (d, J = 7.0 Hz, 1H; OH).
¹³ C NMR (125 MHz, CDCl ₃ , rt): δ 145.8, 144.8, 133.1, 128.61, 128.56, 127.6, 127.5, 125.8, 82.0 (d, J = 160.1 Hz), 77.2 (d, J = 5.6 Hz), 41.6 (d, J = 18.1 Hz).
¹⁹ F NMR (376 MHz, CDCl ₃ , rt): δ -221.2 (m, 1F; CH ₂ F).
HRMS (ESI-TOF) calcd m / z for [C15H14FOCl + Na] ⁺ 287.0609 found 287.0610.

（１８）1-{（1,1'-ビフェニル）-4-イル} -3-フルオロ-1-フェニルプロパン-1-オール(16e)の合成
一般的方法に従い (reaction time = 12 h)、4-（1-フェニルビニル）-1,1'-ビフェニル15e (64.1 mg, 0.250 mmol)、化合物3 (123 mg, 0.376 mmol)、BDN (5.8 mg, 12.5 μmol)、アセトン (4.5 mL) 及び H₂O (0.5 mL) から化合物16eを無色の油として得た (59.3 mg, 0.195 mmol, 77%)。溶離液：ヘキサン/酢酸エチル= 10:1。 (18) Synthesis of 1-{(1,1'-biphenyl) -4-yl} -3-fluoro-1-phenylpropan-1-ol (16e)
According to the general method (reaction time = 12 h), 4- (1-phenylvinyl) -1,1'-biphenyl 15e (64.1 mg, 0.250 mmol), compound 3 (123 mg, 0.376 mmol), BDN (5.8 mg). , 12.5 μmol), acetone (4.5 mL) and H ₂ O (0.5 mL) to give compound 16e as a colorless oil (59.3 mg, 0.195 mmol, 77%). Eluent: Hexane / Ethyl acetate = 10: 1.

¹H NMR (400 MHz, CDCl₃, rt): δ 7.62-7.28 (14H; Ar), 4.62 (apparent dt, J = 47.1 Hz, 6.4 Hz, 2H; CH₂CH₂F), 2.82 (apparent dt, J = 21.5 Hz, 6.4 Hz, 2H; CH₂CH₂F), 2.73 (brs, 1H; OH).
¹³C NMR (125 MHz, CDCl₃, rt): δ 146.2, 145.3, 140.7, 140.1, 128.9, 128.5, 127.5, 127.3, 127.2 (2C), 126.4, 125.9, 82.2 (d, J = 160.3 Hz), 77.4 (overlapped by CDCl₃), 41.7 (d, J = 18.0 Hz).
¹⁹F NMR (376 MHz, CDCl₃, r.t.): δ -221.1 (m, 1F; CH₂F).
HRMS (ESI-TOF) calcd m/z for [C21H19FO+Na]⁺ 329.1312 found 329.1311. ^{1 1} H NMR (400 MHz, CDCl ₃ , rt): δ 7.62-7.28 (14H; Ar), 4.62 (apparent dt, J = 47.1 Hz, 6.4 Hz, 2H; CH ₂ CH ₂ F), 2.82 (apparent dt, J = 21.5 Hz, 6.4 Hz, 2H; CH ₂ CH ₂ F), 2.73 (brs, 1H; OH).
¹³ C NMR (125 MHz, CDCl ₃ , rt): δ 146.2, 145.3, 140.7, 140.1, 128.9, 128.5, 127.5, 127.3, 127.2 (2C), 126.4, 125.9, 82.2 (d, J = 160.3 Hz), 77.4 (overlapped by CDCl ₃ ), 41.7 (d, J = 18.0 Hz).
¹⁹ F NMR (376 MHz, CDCl ₃ , rt): δ -221.1 (m, 1F; CH ₂ F).
HRMS (ESI-TOF) calcd m / z for [C21H19FO + Na] ⁺ 329.1312 found 329.1311.

（１９）3-フルオロ-1-（4-メトキシフェニル）-1-フェニルプロパン-1-オール(16f)の合成
一般的方法に従い (reaction time = 12 h)、1-メトキシ-4-（1-フェニルビニル）ベンゼン15f (52.6 mg, 0.250 mmol)、化合物3 (123 mg, 0.376 mmol)、BDN (5.8 mg, 12.5 μmol)、アセトン (4.5 mL) 及び H₂O (0.5 mL)から化合物 16f を無色の油として得た (42.3 mg, 0.162 mmol, 65%)。溶離液：ヘキサン/酢酸エチル= 10:1。 (19) Synthesis of 3-fluoro-1- (4-methoxyphenyl) -1-phenylpropan-1-ol (16f)
According to the general method (reaction time = 12 h), 1-methoxy-4- (1-phenylvinyl) benzene 15f (52.6 mg, 0.250 mmol), compound 3 (123 mg, 0.376 mmol), BDN (5.8 mg, 12.5). Compound 16f was obtained as a colorless oil from μmol), acetone (4.5 mL) and H ₂ O (0.5 mL) (42.3 mg, 0.162 mmol, 65%). Eluent: Hexane / Ethyl acetate = 10: 1.

¹H NMR (400 MHz, CDCl₃, rt): δ 7.42-7.39 (2H; Ar), 7.34-7.31 (4H; Ar), 7.24 (m, 1H; Ar), 6.87-6.84 (2H; Ar), 4.66-4.45 (2H; CH₂CH₂F), 3.79 (s, 3H, OMe), 2.73 (apparent dt, J = 21.6 Hz, 6.5 Hz, 2H; CH₂CH₂F), 2.52 (d, J = 6.0 Hz, 1H; OH).
¹³C NMR (125 MHz, CDCl₃, rt): δ 158.7, 146.4, 138.6, 128.4, 127.23, 127.19, 125.9, 113.7, 82.2 (d, J = 159.9 Hz), 77.2 (overlapped by CDCl₃), 55.4, 41.8 (d, J = 18.1 Hz).
¹⁹F NMR (376 MHz, CDCl₃, r.t.): δ -221.4 (m, 1F; CH₂F).
HRMS (ESI-TOF) calcd m/z for [C16H17FO2+Na]⁺ 283.1105 found 283.1105. ^{1 1} H NMR (400 MHz, CDCl ₃ , rt): δ 7.42-7.39 (2H; Ar), 7.34-7.31 (4H; Ar), 7.24 (m, 1H; Ar), 6.87-6.84 (2H; Ar), 4.66-4.45 (2H; CH ₂ CH ₂ F), 3.79 (s, 3H, OMe), 2.73 (apparent dt, J = 21.6 Hz, 6.5 Hz, 2H; CH ₂ CH ₂ F), 2.52 (d, J = 6.0 Hz, 1H; OH).
¹³ C NMR (125 MHz, CDCl ₃ , rt): δ 158.7, 146.4, 138.6, 128.4, 127.23, 127.19, 125.9, 113.7, 82.2 (d, J = 159.9 Hz), 77.2 (overlapped by CDCl ₃ ), 55.4, 41.8 (d, J = 18.1 Hz).
¹⁹ F NMR (376 MHz, CDCl ₃ , rt): δ -221.4 (m, 1F; CH ₂ F).
HRMS (ESI-TOF) calcd m / z for [C16H17FO2 + Na] ⁺ 283.1105 found 283.1105.

（２０）3-フルオロ-1-（4-ニトロフェニル）-1-フェニルプロパン-1-オール(16g)の合成
一般的方法に従い (reaction time = 12 h)、1-ニトロ-4-（1-フェニルビニル）ベンゼン15g (56.3 mg, 0.250 mmol)、化合物3 (123 mg, 0.376 mmol)、BDN (5.8 mg, 12.5 μmol)、アセトン (4.5 mL) 及び H₂O (0.5 mL)から化合物 16gを無色の油として得た (34.3 mg, 0.125 mmol, 50%)。溶離液：ヘキサン/酢酸エチル= 4：1。 (20) Synthesis of 3-fluoro-1- (4-nitrophenyl) -1-phenylpropan-1-ol (16 g)
According to the general method (reaction time = 12 h), 1-nitro-4- (1-phenylvinyl) benzene 15 g (56.3 mg, 0.250 mmol), compound 3 (123 mg, 0.376 mmol), BDN (5.8 mg, 12.5). 16 g of compound was obtained as colorless oil from μmol), acetone (4.5 mL) and H ₂ O (0.5 mL) (34.3 mg, 0.125 mmol, 50%). Eluent: Hexane / Ethyl acetate = 4: 1.

¹H NMR (400 MHz, CDCl₃, rt): δ 8.19-8.16 (2H; Ar), 7.64-7.61 (2H; Ar), 7.43-7.35 (4H; Ar), 7.29 (m, 1H; Ar), 4.71-4.50 (2H; CH₂CH₂F), 2.83-2.75 (2H; CH₂CH₂F), 2.82 (brs, 1H; OH).
¹³C NMR (125 MHz, CDCl₃, rt): δ 153.4, 147.0, 145.1, 128.9, 128.0, 126.9, 125.8, 123.7, 81.7 (d, J = 161.3 Hz), 77.4 (overlapped to CDCl₃), 41.4 (d, J = 18.0 Hz).
¹⁹F NMR (376 MHz, CDCl₃, r.t.): δ -220.7 (m, 1F; CH₂F).
HRMS (ESI-TOF) calcd m/z for [C15H14FO3+Na]⁺ 298.0850 found 298.0850. ¹ H NMR (400 MHz, CDCl ₃ , rt): δ 8.19-8.16 (2H; Ar), 7.64-7.61 (2H; Ar), 7.43-7.35 (4H; Ar), 7.29 (m, 1H; Ar), 4.71-4.50 (2H; CH ₂ CH ₂ F), 2.83-2.75 (2H; CH ₂ CH ₂ F), 2.82 (brs, 1H; OH).
¹³ C NMR (125 MHz, CDCl ₃ , rt): δ 153.4, 147.0, 145.1, 128.9, 128.0, 126.9, 125.8, 123.7, 81.7 (d, J = 161.3 Hz), 77.4 (overlapped to CDCl ₃ ), 41.4 ( d, J = 18.0 Hz).
¹⁹ F NMR (376 MHz, CDCl ₃ , rt): δ -220.7 (m, 1F; CH ₂ F).
HRMS (ESI-TOF) calcd m / z for [C15H14FO3 + Na] ⁺ 298.0850 found 298.0850.

（２１）3-フルオロ-1,1-ジ-p-トリルプロパン-1-オール(16h)の合成
一般的方法に従い (reaction time = 12 h)、1,1-ジ-p-トリルエチレン15h (52.1 mg, 0.250 mmol)、化合物3 (123 mg, 0.377 mmol)、BDN (5.8 mg, 12.5 μmol)、アセトン (4.5 mL) 及び H₂O (0.5 mL) から化合物 16hを白い油性固体として得た(51.1 mg, 0.209 mmol, 79%)。溶離液：ヘキサン/酢酸エチル= 10:1。 (21) Synthesis of 3-fluoro-1,1-di-p-tolylpropan-1-ol (16h)
According to the general method (reaction time = 12 h), 1,1-di-p-tolylethylene 15 h (52.1 mg, 0.250 mmol), compound 3 (123 mg, 0.377 mmol), BDN (5.8 mg, 12.5 μmol), Compound 16h was obtained from acetone (4.5 mL) and H ₂ O (0.5 mL) as a white oily solid (51.1 mg, 0.209 mmol, 79%). Eluent: Hexane / Ethyl acetate = 10: 1.

¹H NMR (400 MHz, CDCl₃, rt): δ 7.28 (d, J = 8.1 Hz, 4H; Ar), 7.12 (d, J = 8.1 Hz, 4H; Ar), 4.55 (dt, J = 47.2 Hz, 6.5 Hz, 2H; CH₂CH₂F), 2.72 (dt, J = 21.2 Hz, 6.5 Hz, 2H; CH₂CH₂F), 2.47 (d, J = 5.6 Hz, 1H; OH), 2.32 (s, 6H; Me).
¹³C NMR (125 MHz, CDCl₃, rt): δ 143.6, 136.8, 129.1, 125.8, 82.2 (d, J = 159.9 Hz), 77.2 (overlapped by CDCl₃), 41.8 (d, J = 18.2 Hz), 21.1.
¹⁹F NMR (376 MHz, CDCl₃, r.t.): δ -221.4 (m, 1F; CH₂F).
HRMS (ESI-TOF) calcd m/z for [C17H19FO+Na]⁺ 281.1312 found 281.1310. ^{1 1} H NMR (400 MHz, CDCl ₃ , rt): δ 7.28 (d, J = 8.1 Hz, 4H; Ar), 7.12 (d, J = 8.1 Hz, 4H; Ar), 4.55 (dt, J = 47.2 Hz) , 6.5 Hz, 2H; CH ₂ CH ₂ F), 2.72 (dt, J = 21.2 Hz, 6.5 Hz, 2H; CH ₂ CH ₂ F), 2.47 (d, J = 5.6 Hz, 1H; OH), 2.32 ( s, 6H; Me).
¹³ C NMR (125 MHz, CDCl ₃ , rt): δ 143.6, 136.8, 129.1, 125.8, 82.2 (d, J = 159.9 Hz), 77.2 (overlapped by CDCl ₃ ), 41.8 (d, J = 18.2 Hz), 21.1.
¹⁹ F NMR (376 MHz, CDCl ₃ , rt): δ -221.4 (m, 1F; CH ₂ F).
HRMS (ESI-TOF) calcd m / z for [C17H19FO + Na] ⁺ 281.1312 found 281.1310.

（２２）3-フルオロ-1,1-ビス（4-フルオロフェニル）プロパン-1-オール(16i)の合成
一般的方法に従い (reaction time = 12 h)、4,4 ’-（エテン-1,1-ジイル）ビス（フルオロベンゼン） 15i (54.1 mg, 0.250 mmol)、化合物3 (123 mg, 0.375 mmol)、BDN (5.8 mg, 12.5 μmol)、アセトン (4.5 mL) 及び H₂O (0.5 mL) から化合物 16iを白い油性固体として得た (49.2 mg, 0.185 mmol, 74%)。溶離液：ヘキサン/酢酸エチル= 10:1。 (22) Synthesis of 3-fluoro-1,1-bis (4-fluorophenyl) propanol-1-ol (16i)
According to the general method (reaction time = 12 h), 4,4'-(ethen-1,1-diyl) bis (fluorobenzene) 15i (54.1 mg, 0.250 mmol), compound 3 (123 mg, 0.375 mmol), Compound 16i was obtained as a white oily solid from BDN (5.8 mg, 12.5 μmol), acetone (4.5 mL) and H ₂ O (0.5 mL) (49.2 mg, 0.185 mmol, 74%). Eluent: Hexane / Ethyl acetate = 10: 1.

¹H NMR (400 MHz, CDCl₃, rt): δ 7.39-7.35 (4H; Ar), 7.04-6.99 (4H; Ar), 4.56 (dt, J = 47.1 Hz, 6.2 Hz, 2H; CH₂CH₂F), 2.71 (dt, J = 22.6 Hz, 6.2 Hz, 2H; CH₂CH₂F), 2.64 (d, J = 7.4 Hz, 1H; OH).
¹³C NMR (125 MHz, CDCl₃, rt): δ 162.0 (d, J = 245.0 Hz), 141.9 (d, J = 3.1 Hz), 127.7 (d, J = 8.0 Hz), 115.3 (d, J = 21.3 Hz), 82.0 (d, J = 160.5 Hz), 77.0 (overlapped by CDCl₃), 41.9 (d, J = 18.0 Hz).
¹⁹F NMR (376 MHz, CDCl₃, r.t.): δ -116.4 (m, 2F; ArF), -221.2 (m, 1F; CH₂F).
HRMS (ESI-TOF) calcd m/z for [C15H13F3O+Na]⁺ 289.0811 found 289.0806. ^{1 1} H NMR (400 MHz, CDCl ₃ , rt): δ 7.39-7.35 (4H; Ar), 7.04-6.99 (4H; Ar), 4.56 (dt, J = 47.1 Hz, 6.2 Hz, 2H; CH ₂ CH ₂ F), 2.71 (dt, J = 22.6 Hz, 6.2 Hz, 2H; CH ₂ CH ₂ F), 2.64 (d, J = 7.4 Hz, 1H; OH).
¹³ C NMR (125 MHz, CDCl ₃ , rt): δ 162.0 (d, J = 245.0 Hz), 141.9 (d, J = 3.1 Hz), 127.7 (d, J = 8.0 Hz), 115.3 (d, J = 21.3 Hz), 82.0 (d, J = 160.5 Hz), 77.0 (overlapped by CDCl ₃ ), 41.9 (d, J = 18.0 Hz).
¹⁹ F NMR (376 MHz, CDCl ₃ , rt): δ -116.4 (m, 2F; ArF), -221.2 (m, 1F; CH ₂ F).
HRMS (ESI-TOF) calcd m / z for [C15H13F3O + Na] ⁺ 289.0811 found 289.0806.

（２３）5-（2-フルオロエチル）-10,11-ジヒドロ-5H-ジベンゾ[a、d] [7]アヌレン-5-オール(16j)の合成
一般的方法に従い (reaction time = 12 h)、5-メチレン-10,11-ジヒドロ-5Hジベンゾ[a、d] [7]アヌレン15j (51.6 mg, 0.250 mmol)、化合物3 (123 mg, 0.377 mmol)、BDN (5.8 mg, 12.5 μmol)、アセトン (4.5 mL) 及び H₂O (0.5 mL) から化合物 16j を白い油性固体として得た (37.8 mg, 0.147 mmol, 59%)。溶離液：ヘキサン/酢酸エチル= 10:1。 (23) Synthesis of 5- (2-fluoroethyl) -10,11-dihydro-5H-dibenzo [a, d] [7] annulene-5-ol (16j)
According to the general method (reaction time = 12 h), 5-methylene-10,11-dihydro-5H dibenzo [a, d] [7] anurene 15j (51.6 mg, 0.250 mmol), compound 3 (123 mg, 0.377 mmol). ), BDN (5.8 mg, 12.5 μmol), acetone (4.5 mL) and H ₂ O (0.5 mL) gave compound 16j as a white oily solid (37.8 mg, 0.147 mmol, 59%). Eluent: Hexane / Ethyl acetate = 10: 1.

¹H NMR (400 MHz, CDCl₃, rt): δ 7.96 (dd, J = 8.0 Hz, 1.2 Hz, 2H; Ar), 7.27 (ddd, J = 7.6 Hz, 7.6 Hz, 1.4 Hz, 2H; Ar), 7.21 (dd, J = 7.4 Hz, 7.4 Hz, 1.4 Hz, 2H; Ar), 7.13 (d, J = 7.4 Hz, 2H; Ar), 4.35 (dt, J = 47.2 Hz, 6.2 Hz, 2H; CH₂CH₂F), 3.40-3.32 (2H; ArCH₂CH₂Ar), 3.03-2.95 (2H; ArCH₂CH₂Ar), 2.72 (d, J = 6.2 Hz, 1H; OH), 2.67 (dt, J = 23.6 Hz, 6.2 Hz, 2H; CH₂CH₂F).
¹³C NMR (125 MHz, CDCl₃, rt): δ 143.7, 138.6, 130.5, 127.7, 127.0, 126.6, 81.8 (d, J = 160.5 Hz), 78.1 (d, J = 5.2 Hz), 44.9 (d, J = 17.9 Hz), 34.6.
¹⁹F NMR (376 MHz, CDCl₃, r.t.): δ -220.3 (m, 1F; CH₂F).
HRMS (ESI-TOF) calcd m/z for [C17H17FO+Na]⁺ 279.1156 found 279.1151. ¹ H NMR (400 MHz, CDCl ₃ , rt): δ 7.96 (dd, J = 8.0 Hz, 1.2 Hz, 2H; Ar), 7.27 (ddd, J = 7.6 Hz, 7.6 Hz, 1.4 Hz, 2H; Ar) , 7.21 (dd, J = 7.4 Hz, 7.4 Hz, 1.4 Hz, 2H; Ar), 7.13 (d, J = 7.4 Hz, 2H; Ar), 4.35 (dt, J = 47.2 Hz, 6.2 Hz, 2H; CH ₂ CH ₂ F), 3.40-3.32 (2H; ArCH ₂ CH ₂ Ar), 3.03-2.95 (2H; ArCH ₂ CH ₂ Ar), 2.72 (d, J = 6.2 Hz, 1H; OH), 2.67 (dt, J = 23.6 Hz, 6.2 Hz, 2H; CH ₂ CH ₂ F).
¹³ C NMR (125 MHz, CDCl ₃ , rt): δ 143.7, 138.6, 130.5, 127.7, 127.0, 126.6, 81.8 (d, J = 160.5 Hz), 78.1 (d, J = 5.2 Hz), 44.9 (d, J = 17.9 Hz), 34.6.
¹⁹ F NMR (376 MHz, CDCl ₃ , rt): δ -220.3 (m, 1F; CH ₂ F).
HRMS (ESI-TOF) calcd m / z for [C17H17FO + Na] ⁺ 279.1156 found 279.1151.

（２４）3-フルオロ-1-フェニル-1-（ピリジン-3-イル）プロパン-1-オール(16k)の合成
一般的方法に従い (reaction time = 24 h)、3-（1-フェニルビニル）ピリジン15k (52.6 mg, 0.250 mmol)、化合物3 (123 mg, 0.375 mmol)、BDN (5.8 mg, 12.5 μmol)、アセトン (4.5 mL) 及び H₂O (0.5 mL) から化合物 16kを無色の油として得た (24.1 mg, 0.104 mmol, 42%)。溶離液：ヘキサン/酢酸エチル= 1:1。 (24) Synthesis of 3-fluoro-1-phenyl-1- (pyridin-3-yl) propanol-1-ol (16k)
According to common methods (reaction time = 24 h), 3- (1-phenylvinyl) pyridine 15 k (52.6 mg, 0.250 mmol), compound 3 (123 mg, 0.375 mmol), BDN (5.8 mg, 12.5 μmol), acetone Compound 16k was obtained from (4.5 mL) and H ₂ O (0.5 mL) as colorless oil (24.1 mg, 0.104 mmol, 42%). Eluent: Hexane / Ethyl acetate = 1: 1.

¹H NMR (400 MHz, CDCl₃, rt): δ 8.67 (d, J = 1.8 Hz, 1H; Ar), 8.48 (d, J = 3.6 Hz, 1H; Ar), 7.76 (m, 1H; Ar), 7.76 (d, J = 7.6 Hz, 2H; Ar), 7.36 (dd, J = 7.3 Hz, 7.3 Hz, 2H; Ar), 7.29-7.23 (2H; Ar), 4.70-4.50 (2H; CH₂CH₂F), 2.98 (brs, 1H; OH), 2.82-2.73 (2H; CH₂CH₂F).
¹³C NMR (125 MHz, CDCl₃, rt): δ 148.1, 147.4, 145.5, 142.2, 134.1, 128.7, 127.6, 125.9, 123.3, 81.7 (d, J = 161.0 Hz), 76.0 (d, J = 6.0 Hz), 41.5 (d, J = 18.1 Hz).
¹⁹F NMR (376 MHz, CDCl₃, r.t.): δ -221.2 (m, 1F; CH₂F).
HRMS (ESI-TOF) calcd m/z for [C14H14FNO+Na]⁺ 254.0952 found 254.0954. ¹ H NMR (400 MHz, CDCl ₃ , rt): δ 8.67 (d, J = 1.8 Hz, 1H; Ar), 8.48 (d, J = 3.6 Hz, 1H; Ar), 7.76 (m, 1H; Ar) , 7.76 (d, J = 7.6 Hz, 2H; Ar), 7.36 (dd, J = 7.3 Hz, 7.3 Hz, 2H; Ar), 7.29-7.23 (2H; Ar), 4.70-4.50 (2H; CH ₂ CH) ₂ F), 2.98 (brs, 1H; OH), 2.82-2.73 (2H; CH ₂ CH ₂ F).
¹³ C NMR (125 MHz, CDCl ₃ , rt): δ 148.1, 147.4, 145.5, 142.2, 134.1, 128.7, 127.6, 125.9, 123.3, 81.7 (d, J = 161.0 Hz), 76.0 (d, J = 6.0 Hz) ), 41.5 (d, J = 18.1 Hz).
¹⁹ F NMR (376 MHz, CDCl ₃ , rt): δ -221.2 (m, 1F; CH ₂ F).
HRMS (ESI-TOF) calcd m / z for [C14H14FNO + Na] ⁺ 254.0952 found 254.0954.

（２５）3-フルオロ-1-フェニル-1-（チオフェン-2-イル）プロパン-1-オール(16l)の合成
一般的方法に従い (reaction time = 12 h)、2-（1-フェニルビニル）チオフェン15l (46.6 mg, 0.250 mmol)、化合物3 (123 mg, 0.375 mmol)、BDN (5.8 mg, 12.5 μmol)、アセトン (4.5 mL) 及び H₂O (0.5 mL) から化合物 16lを無色の油として得た (30.7mg, 0.130 mmol, 52%)。溶離液：ヘキサン/酢酸エチル= 10:1。 (25) Synthesis of 3-fluoro-1-phenyl-1- (thiophen-2-yl) propanol-1-ol (16l)
According to common methods (reaction time = 12 h), 2- (1-phenylvinyl) thiophene 15 l (46.6 mg, 0.250 mmol), compound 3 (123 mg, 0.375 mmol), BDN (5.8 mg, 12.5 μmol), acetone From (4.5 mL) and H ₂ O (0.5 mL), 16 l of compound was obtained as colorless oil (30.7 mg, 0.130 mmol, 52%). Eluent: Hexane / Ethyl acetate = 10: 1.

¹H NMR (400 MHz, CDCl₃, rt): δ 7.52-7.49 (2H; Ar), 7.38-7.24 (4H; Ar), 6.97-6.92 (2H; Ar), 4.69-4.48 (2H; CH₂CH₂F), 2.91 (d, J = Hz, 1H; OH), 2.86-2.69 (2H; CH₂CH₂F).
¹³C NMR (125 MHz, CDCl₃, rt): δ 152.2, 145.1, 128.4, 127.6, 126.8, 125.6, 125.3, 124.1, 81.9 (d, J = 160.5 Hz), 76.5 (d, J = 5.8 Hz), 43.4 (d, J = 18.0 Hz).
¹⁹F NMR (376 MHz, CDCl₃, r.t.): δ -221.2 (m, 1F; CH₂F).
HRMS (ESI-TOF) calcd m/z for [C13H13FOS+Na]⁺ 259.0563 found 259.0561. ^{1 1} H NMR (400 MHz, CDCl ₃ , rt): δ 7.52-7.49 (2H; Ar), 7.38-7.24 (4H; Ar), 6.97-6.92 (2H; Ar), 4.69-4.48 (2H; CH ₂ CH) ₂ F), 2.91 (d, J = Hz, 1H; OH), 2.86-2.69 (2H; CH ₂ CH ₂ F).
¹³ C NMR (125 MHz, CDCl ₃ , rt): δ 152.2, 145.1, 128.4, 127.6, 126.8, 125.6, 125.3, 124.1, 81.9 (d, J = 160.5 Hz), 76.5 (d, J = 5.8 Hz), 43.4 (d, J = 18.0 Hz).
¹⁹ F NMR (376 MHz, CDCl ₃ , rt): δ -221.2 (m, 1F; CH ₂ F).
HRMS (ESI-TOF) calcd m / z for [C13H13FOS + Na] ⁺ 259.0563 found 259.0561.

（２６）3-フルオロ-2-メチル-1,1-ジフェニルプロパン-1-オール(16m)の合成
一般的方法に従い (reaction time = 24 h)、プロプ-1-エン-1,1-ジイルジベンゼン15m (48.6 mg, 0.250 mmol)、化合物3 (123 mg, 0.375 mmol)、BDN (9.3 mg, 20.1 μmol)、アセトン (4.5 mL) 及び H₂O (0.5 mL) から化合物16mを無色の油として得た (32.8 mg, 0.134 mmol, 54%)。溶離液：ヘキサン/酢酸エチル= 10:1。 (26) Synthesis of 3-fluoro-2-methyl-1,1-diphenylpropan-1-ol (16m)
According to the general method (reaction time = 24 h), prop-1-ene-1,1-diyldibenzene 15 m (48.6 mg, 0.250 mmol), compound 3 (123 mg, 0.375 mmol), BDN (9.3 mg, 20.1). From μmol), acetone (4.5 mL) and H ₂ O (0.5 mL), 16 m of compound was obtained as colorless oil (32.8 mg, 0.134 mmol, 54%). Eluent: Hexane / Ethyl acetate = 10: 1.

¹H NMR (400 MHz, CDCl₃, rt): δ 7.49 (d, J = 8.3 Hz, 4H; Ar), 7.31 (dd, J = 8.3 Hz, 8.3 Hz, 4H; Ar), 7.19 (t, J = 7.3 Hz, 2H; Ar), 4.56-4.37 (2H; CHCH₂F), 3.01 (m, 1H; CHCH₂F) 2.58 (d, J = 7.9 Hz, 1H; OH), 1.14 (d, J = 6.9 Hz, 3H; Me).
¹³C NMR (125 MHz, CDCl₃, rt): δ 146.1, 145.8, 128.5, 128.4, 126.91, 126.86, 125.6, 125.4, 87.3 (d, J = 163.3 Hz), 79.9 (d, J = 5.3 Hz), 41.4 (d, J = 16.8 Hz), 12.0(d, J = 3.6 Hz).
¹⁹F NMR (376 MHz, CDCl₃, r.t.): δ -229.5 (m, 1F; CH₂F).
HRMS (ESI-TOF) calcd m/z for [C16H17FO+Na]⁺ 267.1156 found 267.1151. ^{1 1} H NMR (400 MHz, CDCl ₃ , rt): δ 7.49 (d, J = 8.3 Hz, 4H; Ar), 7.31 (dd, J = 8.3 Hz, 8.3 Hz, 4H; Ar), 7.19 (t, J) = 7.3 Hz, 2H; Ar), 4.56-4.37 (2H; CHCH ₂ F), 3.01 (m, 1H; CHCH ₂ F) 2.58 (d, J = 7.9 Hz, 1H; OH), 1.14 (d, J = 6.9 Hz, 3H; Me).
¹³ C NMR (125 MHz, CDCl ₃ , rt): δ 146.1, 145.8, 128.5, 128.4, 126.91, 126.86, 125.6, 125.4, 87.3 (d, J = 163.3 Hz), 79.9 (d, J = 5.3 Hz), 41.4 (d, J = 16.8 Hz), 12.0 (d, J = 3.6 Hz).
¹⁹ F NMR (376 MHz, CDCl ₃ , rt): δ -229.5 (m, 1F; CH ₂ F).
HRMS (ESI-TOF) calcd m / z for [C16H17FO + Na] ⁺ 267.1156 found 267.1151.

（２７）1-フルオロ-5-メチル-3,5-ジフェニルヘキサン-3-オール(18a)の合成
一般的方法に従い (reaction time = 18 h)、2,4-ジフェニル-4-メチル-1-ペンテン17a (57.6 mg, 0.250 mmol)、化合物3 (123 mg, 0.376 mmol)、BDN (5.8 mg, 12.5 μmol)、アセトン (4.5 mL) 及び H₂O (0.5 mL)から化合物 18aを無色の油として得た (42.3 mg, 0.148 mmol, 61%)。溶離液：ヘキサン/酢酸エチル= 10:1。 (27) Synthesis of 1-fluoro-5-methyl-3,5-diphenylhexane-3-ol (18a)
According to the general method (reaction time = 18 h), 2,4-diphenyl-4-methyl-1-pentene 17a (57.6 mg, 0.250 mmol), compound 3 (123 mg, 0.376 mmol), BDN (5.8 mg, 12.5). Compound 18a was obtained as a colorless oil from μmol), acetone (4.5 mL) and H ₂ O (0.5 mL) (42.3 mg, 0.148 mmol, 61%). Eluent: Hexane / Ethyl acetate = 10: 1.

¹H NMR (400 MHz, CDCl₃, rt): δ 7.31-7.19 (10H; Ar), 4.40-4.04 (2H; CH₂CH₂F), 2.79 (d, J = 14.8 Hz, 1H; CHHCMe2Ph), 2.33 (d, J = 14.8 Hz, 1H; CHHCMe2Ph), 2.22-1.93 (2H; CH₂CH₂F), 1.75 (d, J = 3.7 Hz, 1H; OH), 1.25 (s, 3H, CH₂CMeMePh), 1.04 (s, 3H, CH₂CMeMePh).
¹³C NMR (125 MHz, CDCl₃, rt): δ 148.7, 146.0, 128.7, 128.1, 126.6, 126.3, 126.1, 125.4, 81.4 (d, J = 159.8 Hz), 76.8 (d, J = 6.5 Hz), 55.9, 45.3 (d, J = 17.8 Hz), 37.9, 33.3, 28.4.
¹⁹F NMR (376 MHz, CDCl₃, r.t.): δ -221.3 (m, 1F; CH₂F).
HRMS (ESI-TOF) calcd m/z for [C19H23FO+Na]⁺ 309.1625 found 309.1626. ^{1 1} H NMR (400 MHz, CDCl ₃ , rt): δ 7.31-7.19 (10H; Ar), 4.40-4.04 (2H; CH ₂ CH ₂ F), 2.79 (d, J = 14.8 Hz, 1H; CHHCMe2Ph), 2.33 (d, J = 14.8 Hz, 1H; CHHCMe2Ph), 2.22-1.93 (2H; CH ₂ CH ₂ F), 1.75 (d, J = 3.7 Hz, 1H; OH), 1.25 (s, 3H, CH ₂ CMeMePh) ), 1.04 (s, 3H, CH ₂ CMeMePh).
¹³ C NMR (125 MHz, CDCl ₃ , rt): δ 148.7, 146.0, 128.7, 128.1, 126.6, 126.3, 126.1, 125.4, 81.4 (d, J = 159.8 Hz), 76.8 (d, J = 6.5 Hz), 55.9, 45.3 (d, J = 17.8 Hz), 37.9, 33.3, 28.4.
¹⁹ F NMR (376 MHz, CDCl ₃ , rt): δ -221.3 (m, 1F; CH ₂ F).
HRMS (ESI-TOF) calcd m / z for [C19H23FO + Na] ⁺ 309.1625 found 309.1626.

（２８）4-フルオロ-2-フェニルブタン-2-オール(18b)の合成
一般的方法に従い (reaction time = 18 h), α-メチルスチレン17b (29.5 mg, 0.250 mmol)、化合物3 (123 mg, 0.375 mmol), BDN (5.8 mg, 12.5 μmol), アセトン (4.5 mL) 及び H₂O (0.5 mL) から化合物 18bを無色の油として得た (23.0 mg, 0.137 mmol, 55%)。溶離液：ヘキサン/酢酸エチル= 4：1。 (28) Synthesis of 4-fluoro-2-phenylbutan-2-ol (18b)
According to common methods (reaction time = 18 h), α-methylstyrene 17b (29.5 mg, 0.250 mmol), compound 3 (123 mg, 0.375 mmol), BDN (5.8 mg, 12.5 μmol), acetone (4.5 mL) and Compound 18b was obtained from H ₂ O (0.5 mL) as a colorless oil (23.0 mg, 0.137 mmol, 55%). Eluent: Hexane / Ethyl acetate = 4: 1.

¹H NMR (400 MHz, CDCl₃, rt): δ 7.46-7.25 (5H; Ar), 4.61-4.39 (2H; CH₂CH₂F), 2.36-2.13 (3H; CH₂CH₂F, OH), 1.62 (s, 3H, Me).
¹³C NMR (125 MHz, CDCl₃, rt): δ 147.2, 128.5, 127.0, 124.7, 82.0 (d, J = 160.5 Hz), 74.1 (d, J = 4.2 Hz), 43.7 (d, J = 17.7 Hz), 30.7.
¹⁹F NMR (376 MHz, CDCl₃, r.t.): δ -220.5 (m, 1F; CH₂F).
HRMS (ESI-TOF) calcd m/z for [C10H13FO+Na]⁺ 191.0843 found 191.0842. ¹ H NMR (400 MHz, CDCl ₃ , rt): δ 7.46-7.25 (5H; Ar), 4.61-4.39 (2H; CH ₂ CH ₂ F), 2.36-2.13 (3H; CH ₂ CH ₂ F, OH) , 1.62 (s, 3H, Me).
¹³ C NMR (125 MHz, CDCl ₃ , rt): δ 147.2, 128.5, 127.0, 124.7, 82.0 (d, J = 160.5 Hz), 74.1 (d, J = 4.2 Hz), 43.7 (d, J = 17.7 Hz) ), 30.7.
¹⁹ F NMR (376 MHz, CDCl ₃ , rt): δ -220.5 (m, 1F; CH ₂ F).
HRMS (ESI-TOF) calcd m / z for [C10H13FO + Na] ⁺ 191.0843 found 191.0842.

（２９）1-フルオロ-4-メチル-3-フェニルペンタン-3-オール(18c)の合成
一般的方法に従い (reaction time = 18 h), （3-メチルブト-1-エン-2-イル）ベンゼン17c (46.6 mg, 0.250 mmol)、化合物3 (123 mg, 0.377 mmol)、BDN (5.8 mg, 12.5 μmol)、アセトン (4.5 mL) 及び H₂O (0.5 mL) から化合物18cを無色の油として得た (27.9 mg, 0.142 mmol, 57%)。溶離液：ヘキサン/酢酸エチル= 10:1。 (29) Synthesis of 1-fluoro-4-methyl-3-phenylpentane-3-ol (18c)
According to the general method (reaction time = 18 h), (3-methylbut-1-en-2-yl) benzene 17c (46.6 mg, 0.250 mmol), compound 3 (123 mg, 0.377 mmol), BDN (5.8 mg, Compound 18c was obtained as a colorless oil from 12.5 μmol), acetone (4.5 mL) and H ₂ O (0.5 mL) (27.9 mg, 0.142 mmol, 57%). Eluent: Hexane / Ethyl acetate = 10: 1.

¹H NMR (400 MHz, CDCl₃, rt): δ 7.38-7.32 (4H; Ar), 7.24 (m, 1H; Ar), 4.46-4.31 (2H; CH₂CH₂F), 2.45 (m, 1H; CHMe2), 2.26-2.00 (3H; CH₂CH₂F, OH), 1.01 (d, J = 6.8 Hz, 3H, CHMeMe), 0.71 (d, J = 6.8 Hz, 3H, CHMeMe).
¹³C NMR (125 MHz, CDCl₃, rt): δ 144.6, 128.2, 126.7, 125.7, 82.6 (d, J = 159.5 Hz), 78.4 (d, J = 5.0 Hz), 39.7 (d, J = 17.6 Hz), 38.6, 17.3, 16.7.
¹⁹F NMR (376 MHz, CDCl₃, r.t.): δ -220.6 (m, 1F; CH₂F).
HRMS (ESI-TOF) calcd m/z for [C12H17FO+Na]⁺ 219.1156 found 219.1157. ¹ H NMR (400 MHz, CDCl ₃ , rt): δ 7.38-7.32 (4H; Ar), 7.24 (m, 1H; Ar), 4.46-4.31 (2H; CH ₂ CH ₂ F), 2.45 (m, 1H) CHMe2), 2.26-2.00 (3H; CH ₂ CH ₂ F, OH), 1.01 (d, J = 6.8 Hz, 3H, CHMeMe), 0.71 (d, J = 6.8 Hz, 3H, CHMeMe).
¹³ C NMR (125 MHz, CDCl ₃ , rt): δ 144.6, 128.2, 126.7, 125.7, 82.6 (d, J = 159.5 Hz), 78.4 (d, J = 5.0 Hz), 39.7 (d, J = 17.6 Hz) ), 38.6, 17.3, 16.7.
¹⁹ F NMR (376 MHz, CDCl ₃ , rt): δ -220.6 (m, 1F; CH ₂ F).
HRMS (ESI-TOF) calcd m / z for [C12H17FO + Na] ⁺ 219.1156 found 219.1157.

（３０）1-シクロヘキシル-3-フルオロ-1-フェニルプロパン-1-オール(18d)の合成
一般的方法に従い (reaction time = 18 h)、（1-シクロヘキシルビニル）ベンゼン17d (46.6 mg, 0.250 mmol)、化合物3 (123 mg, 0.377 mmol)、BDN (5.8 mg, 12.5 μmol)、アセトン (4.5 mL) 及び H₂O (0.5 mL) から化合物18dを無色の油として得た (38.9 mg, 0.165 mmol, 66%)。溶離液：ヘキサン/酢酸エチル= 10:1。 (30) Synthesis of 1-cyclohexyl-3-fluoro-1-phenylpropan-1-ol (18d)
According to common methods (reaction time = 18 h), (1-cyclohexylvinyl) benzene 17d (46.6 mg, 0.250 mmol), compound 3 (123 mg, 0.377 mmol), BDN (5.8 mg, 12.5 μmol), acetone (4.5) Compound 18d was obtained as a colorless oil from mL) and H ₂ O (0.5 mL) (38.9 mg, 0.165 mmol, 66%). Eluent: Hexane / Ethyl acetate = 10: 1.

¹H NMR (400 MHz, CDCl₃, rt): δ 7.36-7.31 (4H; Ar), 7.24 (m, 1H; Ar), 4.49-4.29 (2H; CH₂CH₂F), 2.51- 2.12 (3H; CH₂CH₂F, OH), 1.97-1.60 (5H, cyclohexyl’s H), 1.37-0.92 (6H, cyclohexyl’s H).
¹³C NMR (125 MHz, CDCl₃, rt): δ 144.6, 128.1, 126.6, 125.8, 82.6 (d, J = 159.2 Hz), 78.4 (d, J = 5.0 Hz), 48.9, 39.3 (d, J = 18.1 Hz), 27.1, 26.71, 26.69 (2C), 26.5.
¹⁹F NMR (376 MHz, CDCl₃, r.t.): δ -220.6 (m, 1F; CH₂F).
HRMS (ESI-TOF) calcd m/z for [C15H21FO+Na]⁺ 259.1469 found 259.1466. ¹ H NMR (400 MHz, CDCl ₃ , rt): δ 7.36-7.31 (4H; Ar), 7.24 (m, 1H; Ar), 4.49-4.29 (2H; CH ₂ CH ₂ F), 2.51- 2.12 (3H) CH ₂ CH ₂ F, OH), 1.97-1.60 (5H, cyclohexyl's H), 1.37-0.92 (6H, cyclohexyl's H).
¹³ C NMR (125 MHz, CDCl ₃ , rt): δ 144.6, 128.1, 126.6, 125.8, 82.6 (d, J = 159.2 Hz), 78.4 (d, J = 5.0 Hz), 48.9, 39.3 (d, J = 18.1 Hz), 27.1, 26.71, 26.69 (2C), 26.5.
¹⁹ F NMR (376 MHz, CDCl ₃ , rt): δ -220.6 (m, 1F; CH ₂ F).
HRMS (ESI-TOF) calcd m / z for [C15H21FO + Na] ⁺ 259.1469 found 259.1466.

（３１）1-（2-フルオロエチル）-2,3-ジヒドロ-1H-インデン-1-オール(20a)の合成
一般的方法に従い (reaction time = 18 h)、1-メチレン-2,3-ジヒドロ-1H-インデン19a (32.5mg, 0.250 mmol)、化合物3 (123 mg, 0.374 mmol)、BDN (5.8 mg, 12.5 μmol)、アセトン (4.5 mL) 及び H₂O (0.5 mL)から化合物 20aを無色の油として得た (27.1 mg, 0.150 mmol, 60%)。溶離液：ヘキサン/酢酸エチル= 4：1。 (31) Synthesis of 1- (2-fluoroethyl) -2,3-dihydro-1H-indene-1-ol (20a)
According to the general method (reaction time = 18 h), 1-methylene-2,3-dihydro-1H-inden 19a (32.5 mg, 0.250 mmol), compound 3 (123 mg, 0.374 mmol), BDN (5.8 mg, 12.5). Compound 20a was obtained as a colorless oil from μmol), acetone (4.5 mL) and H ₂ O (0.5 mL) (27.1 mg, 0.150 mmol, 60%). Eluent: Hexane / Ethyl acetate = 4: 1.

¹H NMR (400 MHz, CDCl₃, rt): δ 7.34 (m, 1H; Ar), 7.29-7.23 (3H; Ar), 4.84-4.56 (2H; CH₂CH₂F), 3.07- 2.81 (2H; ArCH₂CH₂), 2.42-2.11 (4H; ArCH₂CH₂, CH₂CH₂F), 1.99 (d, J = 2.5 Hz, 1H; OH).
¹³C NMR (125 MHz, CDCl₃, rt): δ 146.9, 143.0, 128.6, 127.0, 125.2, 122.8, 82.4 (d, J = 4.2 Hz), 81.7 (d, J = 161.8 Hz), 40.6, 40.0 (d, J = 18.4 Hz), 29.5.
¹⁹F NMR (376 MHz, CDCl₃, r.t.): δ -219.6 (m, 1F; CH₂F).
HRMS (ESI-TOF) calcd m/z for [C11H13FO+Na]⁺ 203.0843 found 203.0840. ¹ H NMR (400 MHz, CDCl ₃ , rt): δ 7.34 (m, 1H; Ar), 7.29-7.23 (3H; Ar), 4.84-4.56 (2H; CH ₂ CH ₂ F), 3.07-2.81 (2H) ArCH ₂ CH ₂ ), 2.42-2.11 (4H; ArCH ₂ CH ₂ , CH ₂ CH ₂ F), 1.99 (d, J = 2.5 Hz, 1H; OH).
¹³ C NMR (125 MHz, CDCl ₃ , rt): δ 146.9, 143.0, 128.6, 127.0, 125.2, 122.8, 82.4 (d, J = 4.2 Hz), 81.7 (d, J = 161.8 Hz), 40.6, 40.0 ( d, J = 18.4 Hz), 29.5.
¹⁹ F NMR (376 MHz, CDCl ₃ , rt): δ -219.6 (m, 1F; CH ₂ F).
HRMS (ESI-TOF) calcd m / z for [C11H13FO + Na] ⁺ 203.0843 found 203.0840.

（３２）1-（2-フルオロエチル）-1,2,3,4-テトラヒドロナフタレン-1-オール(20b)の合成
一般的方法に従い (reaction time = 18 h)、1-メチレン-1,2,3,4-テトラヒドロナフタレン19b (36.1 mg, 0.250 mmol)、化合物3 (123 mg, 0.376 mmol)、BDN (5.8 mg, 12.5 μmol)、アセトン (4.5 mL) 及び H₂O(0.5 mL) から化合物 20bを無色の油として得た (35.1 mg, 0.181 mmol, 72%)。溶離液：ヘキサン/酢酸エチル= 4：1。 (32) Synthesis of 1- (2-fluoroethyl) -1,2,3,4-tetrahydronaphthalene-1-ol (20b)
According to the general method (reaction time = 18 h), 1-methylene-1,2,3,4-tetrahydronaphthalene 19b (36.1 mg, 0.250 mmol), compound 3 (123 mg, 0.376 mmol), BDN (5.8 mg, 5.8 mg, Compound 20b was obtained as a colorless oil from 12.5 μmol), acetone (4.5 mL) and H ₂ O (0.5 mL) (35.1 mg, 0.181 mmol, 72%). Eluent: Hexane / Ethyl acetate = 4: 1.

¹H NMR (400 MHz, CDCl₃, rt): δ 7.53 (m, 1H; Ar), 7.24-7.17 (2H; Ar), 7.09 (d, J = 7.1 Hz, 1H; Ar), 4.80- 4.52 (2H; CH₂CH₂F), 2.88-2.74 (2H; ArCH₂CH₂), 2.37-1.84 (7H; ArCH₂CH₂, CH₂C, CH₂CH₂F, OH).
¹³C NMR (125 MHz, CDCl₃, rt): δ 141.9, 136.7, 129.2, 127.5, 126.5, 126.2, 81.4 (d, J = 161.7 Hz), 71.7 (d, J = 4.4 Hz), 42.2 (d, J = 18.2 Hz), 36.7, 29.7, 19.9.
¹⁹F NMR (376 MHz, CDCl₃, r.t.): δ -219.0 (m, 1F; CH₂F).
HRMS (ESI-TOF) calcd m/z for [C12H15FO+Na]⁺ 217.0999 found 217.0999. ¹ H NMR (400 MHz, CDCl ₃ , rt): δ 7.53 (m, 1H; Ar), 7.24-7.17 (2H; Ar), 7.09 (d, J = 7.1 Hz, 1H; Ar), 4.80-4.52 ( 2H; CH ₂ CH ₂ F), 2.88-2.74 (2H; ArCH ₂ CH ₂ ), 2.37-1.84 (7H; ArCH ₂ CH ₂ , CH ₂ C, CH ₂ CH ₂ F, OH).
¹³ C NMR (125 MHz, CDCl ₃ , rt): δ 141.9, 136.7, 129.2, 127.5, 126.5, 126.2, 81.4 (d, J = 161.7 Hz), 71.7 (d, J = 4.4 Hz), 42.2 (d, J = 18.2 Hz), 36.7, 29.7, 19.9.
¹⁹ F NMR (376 MHz, CDCl ₃ , rt): δ -219.0 (m, 1F; CH ₂ F).
HRMS (ESI-TOF) calcd m / z for [C12H15FO + Na] ⁺ 217.0999 found 217.0999.

（３３）4-（2-フルオロエチル）チオクロマン-4-オール(20c)の合成
一般的方法に従い (reaction time = 18 h)、4-メチレンチオクロマン19c (40.6 mg, 0.250 mmol)、化合物3 (123 mg, 0.377 mmol)、BDN (5.8 mg, 12.5 μmol)、アセトン (4.5 mL) 及び H₂O (0.5 mL) から化合物 20cを無色の油として得た (40.5 mg, 0.191 mmol, 76%)。溶離液：ヘキサン/酢酸エチル= 4：1。 (33) Synthesis of 4- (2-fluoroethyl) thiochroman-4-ol (20c)
According to common methods (reaction time = 18 h), 4-methylenethiochroman 19c (40.6 mg, 0.250 mmol), compound 3 (123 mg, 0.377 mmol), BDN (5.8 mg, 12.5 μmol), acetone (4.5 mL) And H ₂ O (0.5 mL) gave compound 20c as a colorless oil (40.5 mg, 0.191 mmol, 76%). Eluent: Hexane / Ethyl acetate = 4: 1.

¹H NMR (400 MHz, CDCl₃, rt): δ 7.69 (m, 1H; Ar), 7.15-7.08 (3H; Ar), 4.81-4.50 (2H; CH₂CH₂F), 3.16- 3.03 (2H; SCH₂CH₂), 2.43-2.10 (4H; SCH₂CH₂, CH₂CH₂F), 2.14 (brs, 1H; OH).
¹³C NMR (125 MHz, CDCl₃, rt): δ 139.2, 132.7, 127.9, 126.6, 125.9, 124.5, 81.1 (d, J = 161.6 Hz), 71.0 (d, J = 3.3 Hz), 39.9 (d, J = 18.2 Hz), 35.5, 23.3.
¹⁹F NMR (376 MHz, CDCl₃, r.t.): δ -218.9 (m, 1F; CH₂F).
HRMS (ESI-TOF) calcd m/z for [C11H12FOS+Na]⁺ 235.0563 found 235.0560. ¹ H NMR (400 MHz, CDCl ₃ , rt): δ 7.69 (m, 1H; Ar), 7.15-7.08 (3H; Ar), 4.81-4.50 (2H; CH ₂ CH ₂ F), 3.16- 3.03 (2H) SCH ₂ CH ₂ ), 2.43-2.10 (4H; SCH ₂ CH ₂ , CH ₂ CH ₂ F), 2.14 (brs, 1H; OH).
¹³ C NMR (125 MHz, CDCl ₃ , rt): δ 139.2, 132.7, 127.9, 126.6, 125.9, 124.5, 81.1 (d, J = 161.6 Hz), 71.0 (d, J = 3.3 Hz), 39.9 (d, J = 18.2 Hz), 35.5, 23.3.
¹⁹ F NMR (376 MHz, CDCl ₃ , rt): δ -218.9 (m, 1F; CH ₂ F).
HRMS (ESI-TOF) calcd m / z for [C11H12FOS + Na] ⁺ 235.0563 found 235.0560.

（３４）（8R、9S、13S、14S）-3-（3-フルオロ-1-ヒドロキシプロピル）-13-メチル-6,7,8,9,11,12,13,14,15,16-デカヒドロ-17Hシクロペンタ[ a]フェナントレン-17-ワン (22)の合成
一般的方法に従い (reaction time = 12 h)、（8R、9S、13S、14S）-13-メチル-3-ビニル-6,7,8,9,11,12,13,14,15,16-デカヒドロ-17H-シクロペンタ[a]フェナントレン-17-ワン21 (70.1 mg, 0.250 mmol)、化合物3(123 mg, 0.376 mmol)、BDN (5.8 mg, 12.5 μmol)、アセトン (4.5 mL) 及び H₂O (0.5 mL) から化合物 22を無色の油として得た(24.7 mg, 0.0747 mmol, 30%)。溶離液：ヘキサン/酢酸エチル= 1:1。 (34) (8R, 9S, 13S, 14S) -3- (3-Fluoro-1-hydroxypropyl) -13-methyl-6,7,8,9,11,12,13,14,15,16- Synthesis of Decahydro-17H Cyclopentane [a] Phenanthrene-17-One (22)
According to the general method (reaction time = 12 h), (8R, 9S, 13S, 14S) -13-methyl-3-vinyl-6,7,8,9,11,12,13,14,15,16- Decahydro-17H-Cyclopentane [a] Phenanthrene-17-One 21 (70.1 mg, 0.250 mmol), Compound 3 (123 mg, 0.376 mmol), BDN (5.8 mg, 12.5 μmol), Acetone (4.5 mL) and H ₂ O Compound 22 was obtained from (0.5 mL) as a colorless oil (24.7 mg, 0.0747 mmol, 30%). Eluent: Hexane / Ethyl acetate = 1: 1.

¹H NMR (400 MHz, CDCl₃, rt): δ 7.30 (d, J = Hz, 1H; Ar), 7.15 (d, J = Hz, 1H; Ar), 7.12 (s, 1H; Ar), 4.87 (m, 1H; CH₂CHOH), 4.78-4.44 (2H; CH₂F), 2.95-2.91 (2H; steroid’s H), 2.54-2.42 (2H; steroid’s H), 2.31 (m, 1H; steroid’s H), 2.23-1.95 (7H; CH₂CHOH, OH, steroid’s H), 1.69-1.40 (6H; steroid’s H), 0.91 (s, 3H; Me).
¹³C NMR (125 MHz, CDCl₃, rt): δ 221.1, 141.6, 139.5, 136.9, 126.5 (apparent d), 125.8 (apparent d), 123.3, 81.6 (d, J = 162.1 Hz), 70.7, 50.6, 48.1, 44.5, 39.6 (d, J = 19.6 Hz), 38.3, 36.0, 31.7, 29.6 (apparent d), 26.6, 25.8, 21.7, 13.9.
¹⁹F NMR (376 MHz, CDCl₃, r.t.): δ -222.3 (m, 1F; CH₂F).
HRMS (ESI-TOF) calcd m/z for [C21H27FO2+Na]⁺ 353.1887 found 353.1886. ¹ H NMR (400 MHz, CDCl ₃ , rt): δ 7.30 (d, J = Hz, 1H; Ar), 7.15 (d, J = Hz, 1H; Ar), 7.12 (s, 1H; Ar), 4.87 (m, 1H; CH ₂ CHOH), 4.78-4.44 (2H; CH ₂ F), 2.95-2.91 (2H; steroid's H), 2.54-2.42 (2H; steroid's H), 2.31 (m, 1H; steroid's H) , 2.23-1.95 (7H; CH ₂ CHOH, OH, steroid's H), 1.69-1.40 (6H; steroid's H), 0.91 (s, 3H; Me).
¹³ C NMR (125 MHz, CDCl ₃ , rt): δ 221.1, 141.6, 139.5, 136.9, 126.5 (apparent d), 125.8 (apparent d), 123.3, 81.6 (d, J = 162.1 Hz), 70.7, 50.6, 48.1, 44.5, 39.6 (d, J = 19.6 Hz), 38.3, 36.0, 31.7, 29.6 (apparent d), 26.6, 25.8, 21.7, 13.9.
¹⁹ F NMR (376 MHz, CDCl ₃ , rt): δ -222.3 (m, 1F; CH ₂ F).
HRMS (ESI-TOF) calcd m / z for [C21H27FO2 + Na] ⁺ 353.1887 found 353.1886.

（３５）4-（2-フルオロエチル）-2-フェニルクロマン-4-オール(24)の合成
一般的方法に従い (reaction time = 24 h)、4-メチレン-2-フェニルクロマン23 (55.6 mg, 0.250 mmol)、化合物3 (123 mg, 0.376 mmol)、BDN (5.8 mg, 12.5 μmol)、アセトン (4.5 mL) 及び H₂O (0.5 mL) から化合物24を無色の油として得た (50.5 mg, 0.185 mmol, 74%)。溶離液：ヘキサン/酢酸エチル= 4：1。 (35) Synthesis of 4- (2-fluoroethyl) -2-phenylchroman-4-ol (24)
According to the general method (reaction time = 24 h), 4-methylene-2-phenylchroman 23 (55.6 mg, 0.250 mmol), compound 3 (123 mg, 0.376 mmol), BDN (5.8 mg, 12.5 μmol), acetone ( Compound 24 was obtained as a colorless oil from 4.5 mL) and H ₂ O (0.5 mL) (50.5 mg, 0.185 mmol, 74%). Eluent: Hexane / Ethyl acetate = 4: 1.

¹H NMR (400 MHz, CDCl₃, rt): δ 7.50-7.33 (6H; Ar), 7.27 (m,1H; Ar), 7.03-6.99 (2H; Ar), 5.23 (dd, J = 11.9 Hz, 1.7 Hz, 1H; OCHCH₂), 4.77-4.51 (2H; CH₂CH₂F), 2.63 (m, 1H; CHHCH₂F), 2.32-2.14 (4H; CHHCH₂F, OH, OCHCH₂).
¹³C NMR (125 MHz, CDCl₃, rt): δ 155.0, 140.9, 130.0, 128.7, 128.2, 126.34, 126.25, 126.0, 121.4, 118.2, 81.1 (d, J = 163.0 Hz), 74.4, 68.3 (d, J = 3.6 Hz), 43.2 (d, J = 0.5 Hz), 41.4 (d, J = 18.7 Hz).
¹⁹F NMR (376 MHz, CDCl₃, r.t.): δ -218.5 (m, 1F; CH₂F).
HRMS (ESI-TOF) calcd m/z for [C17H17FO2+Na]⁺ 295.1105 found 295.1105. ^{1 1} H NMR (400 MHz, CDCl ₃ , rt): δ 7.50-7.33 (6H; Ar), 7.27 (m, 1H; Ar), 7.03-6.99 (2H; Ar), 5.23 (dd, J = 11.9 Hz, 1.7 Hz, 1H; OCHCH ₂ ), 4.77-4.51 (2H; CH ₂ CH ₂ F), 2.63 (m, 1H; CHHCH ₂ F), 2.32-2.14 (4H; CHHCH ₂ F, OH, OCHCH ₂ ).
¹³ C NMR (125 MHz, CDCl ₃ , rt): δ 155.0, 140.9, 130.0, 128.7, 128.2, 126.34, 126.25, 126.0, 121.4, 118.2, 81.1 (d, J = 163.0 Hz), 74.4, 68.3 (d,, J = 3.6 Hz), 43.2 (d, J = 0.5 Hz), 41.4 (d, J = 18.7 Hz).
¹⁹ F NMR (376 MHz, CDCl ₃ , rt): δ -218.5 (m, 1F; CH ₂ F).
HRMS (ESI-TOF) calcd m / z for [C17H17FO2 + Na] ⁺ 295.1105 found 295.1105.

（３６）4- {3-フルオロ-1-ヒドロキシ-1-（3,5,5,8,8-ペンタメチル-5,6,7,8-テトラヒドロナフタレン-2-イル）プロピル}安息香酸(26)の合成
一般的方法に従い (reaction time = 24 h)、ベキサロテン25 (87.1 mg, 0.250 mmol)、化合物3 (123 mg, 0.376 mmol)、BDN (5.8 mg, 12.5 μmol)、アセトン (4.5 mL) 及び H₂O (0.5 mL) から、シリカゲルのフラッシュカラムクロマトグラフィー（ヘキサン/酢酸エチル= 1：1）で精製し、分取HPLCとCH₂Cl₂及びヘキサンで再沈殿して、化合物26を白色固体として得た(45.2 mg, 0.113 mmol, 45%)。 (36) 4- {3-Fluoro-1-hydroxy-1- (3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalene-2-yl) propyl} benzoic acid (26) ) Synthesis
According to common methods (reaction time = 24 h), hexane 25 (87.1 mg, 0.250 mmol), compound 3 (123 mg, 0.376 mmol), BDN (5.8 mg, 12.5 μmol), acetone (4.5 mL) and H ₂ O. From (0.5 mL), silica gel was purified by flash column chromatography (hexane / ethyl acetate = 1: 1) and reprecipitated by preparative HPLC and CH ₂ Cl ₂ and hexane to give compound 26 as a white solid. (45.2 mg, 0.113 mmol, 45%).

¹H NMR (400 MHz, CDCl₃, rt): δ 11.65 (brs, 1H, COOH), 8.04 (d, J = 8.4 Hz, 2H; Ar), 7.51 (s, 1H; Ar), 7.42 (d, J = 8.4 Hz, 2H; Ar), 6.99 (s, 1H; Ar), 4.69-4.37 (2H; CH₂CH₂F), 2.86-2.62 (2H; CH₂CH₂F), 2.49 (brs, 1H; OH), 1.92 (s, 3H; ArMe), 1.72-1.68 (4H; methylene’H), 1.33 (6H; Me), 1.26 (s, 3H; Me), 1.25 (s, 3H;
Me).
¹³C NMR (125 MHz, CDCl₃, rt): δ 172.1, 152.1, 144.7, 141.9, 139.8, 133.9, 131.1, 130.2, 127.9, 126.2, 123.9, 81.8 (d, J = 160.5 Hz), 78.0 (d, J = 7.1 Hz), 42.7 (d, J = 18.8 Hz), 35.3, 35.2, 34.2, 34.0, 32.2, 32.1, 31.9, 31.7, 21.1.
¹⁹F NMR (376 MHz, CDCl₃, r.t.): δ -221.2 (m, 1F; CH₂F).
HRMS (ESI-TOF) calcd m/z for [C25H31FO3+Na]⁺ 421.2149 found 421.2147. ¹ H NMR (400 MHz, CDCl ₃ , rt): δ 11.65 (brs, 1H, COOH), 8.04 (d, J = 8.4 Hz, 2H; Ar), 7.51 (s, 1H; Ar), 7.42 (d, J = 8.4 Hz, 2H; Ar), 6.99 (s, 1H; Ar), 4.69-4.37 (2H; CH ₂ CH ₂ F), 2.86-2.62 (2H; CH ₂ CH ₂ F), 2.49 (brs, 1H) OH), 1.92 (s, 3H; ArMe), 1.72-1.68 (4H; methylene'H), 1.33 (6H; Me), 1.26 (s, 3H; Me), 1.25 (s, 3H;
Me).
¹³ C NMR (125 MHz, CDCl ₃ , rt): δ 172.1, 152.1, 144.7, 141.9, 139.8, 133.9, 131.1, 130.2, 127.9, 126.2, 123.9, 81.8 (d, J = 160.5 Hz), 78.0 (d, J = 7.1 Hz), 42.7 (d, J = 18.8 Hz), 35.3, 35.2, 34.2, 34.0, 32.2, 32.1, 31.9, 31.7, 21.1.
¹⁹ F NMR (376 MHz, CDCl ₃ , rt): δ -221.2 (m, 1F; CH ₂ F).
HRMS (ESI-TOF) calcd m / z for [C25H31FO3 + Na] ⁺ 421.2149 found 421.2147.

〔実施例４〕モノフルオロアルキル化反応
（１）モノフルオロアルキル化の一般的方法
窒素雰囲気下、1-フェニルビニルアセテート（0.250 mmol）、モノフルオロアルキル化剤（128.0 mg, 0.375 mmol）、2-tBuBDN（7.19 mg, 12.5 μmol）のアセトン（4.75 mL）・水（0.25 mL）混合溶液に、425 nmのLEDランプを照射し、室温条件で24時間撹拌した。反応混合物から溶媒を留去し、カラムクロマトグラフィー（ペンタン・ジエチルエーテル）で精製した。 [Example 4] Monofluoroalkylation reaction (1) General method of monofluoroalkylation
Mix 1-phenylvinyl acetate (0.250 mmol), monofluoroalkylating agent (128.0 mg, 0.375 mmol), 2-tBuBDN (7.19 mg, 12.5 μmol) with acetone (4.75 mL) and water (0.25 mL) under a nitrogen atmosphere. The solution was irradiated with a 425 nm LED lamp and stirred at room temperature for 24 hours. The solvent was distilled off from the reaction mixture, and the mixture was purified by column chromatography (pentane diethyl ether).

（２）各種モノフルオロアルキル化物の合成
上記の一般的方法に従い、対応する芳香族ビニルアセテートを用いることで、下記のモノフルオロアルキル化物を合成した。
¹H NMR (400 MHz, CDCl₃, rt): δ 8.04 (d, 3JHH = 8.3 Hz, 2 H; Ar), 7.70 (d, 3JHH = 8.3 Hz, 2 H; Ar), 7.63 (d, 3JHH = 7.4 Hz, 2 H; Ar), 7.48 (t, 3JHH = 7.4 Hz, 2 H; Ar), 7.41 (t, 3JHH = 7.4 Hz, 1 H; Ar), 5.34 (dq, 2JHF = 47.6 Hz, 3JHH = 6.2 Hz, 1 H; CHF), 3.55 (m, 1 H; CHH), 3.12 (m, 1 H; CHH), 1.50 (dd, 3JHF = 24.1 Hz, 3JHH = 6.2 Hz, 3 H; CH3); ¹³C NMR (126 MHz, CDCl₃, rt): δ 196.6 (d, 3JCF = 6.7 Hz), 146.3, 139.9, 135.6, 129.1 (2 C), 128.9 (2C), 128.5, 127.5 (2C), 127.4 (2C), 87.4 (d, 1JCF = 165.5 Hz), 45.6 (d, 2JCF = 22.8 Hz), 21.4 (d, 2JCF = 22.5 Hz); ¹⁹F NMR (376 MHz, CDCl₃, rt): δ -172.5 (m, 1 F); HRMS (ESI-TOF) calcd m/z for [C16H15FO+Na]⁺ 265.0999, found 265.0997. (2) Synthesis of various monofluoroalkyl compounds The following monofluoroalkyl compounds were synthesized by using the corresponding aromatic vinyl acetate according to the above general method.
¹ H NMR (400 MHz, CDCl ₃ , rt): δ 8.04 (d, 3JHH = 8.3 Hz, 2 H; Ar), 7.70 (d, 3JHH = 8.3 Hz, 2 H; Ar), 7.63 (d, 3JHH = 7.4 Hz, 2 H; Ar), 7.48 (t, 3JHH = 7.4 Hz, 2 H; Ar), 7.41 (t, 3JHH = 7.4 Hz, 1 H; Ar), 5.34 (dq, 2JHF = 47.6 Hz, 3JHH = 6.2 Hz, 1 H; CHF), 3.55 (m, 1 H; CHH), 3.12 (m, 1 H; CHH), 1.50 (dd, 3JHF = 24.1 Hz, 3JHH = 6.2 Hz, 3 H; CH3); ¹³ C NMR (126 MHz, CDCl ₃ , rt): δ 196.6 (d, 3JCF = 6.7 Hz), 146.3, 139.9, 135.6, 129.1 (2 C), 128.9 (2C), 128.5, 127.5 (2C), 127.4 (2C) ), 87.4 (d, 1JCF = 165.5 Hz), 45.6 (d, 2JCF = 22.8 Hz), 21.4 (d, 2JCF = 22.5 Hz); ¹⁹ F NMR (376 MHz, CDCl ₃ , rt): δ -172.5 (m) , 1 F); HRMS (ESI-TOF) calcd m / z for [C16H15FO + Na] ⁺ 265.0999, found 265.0997.

¹H NMR (400 MHz, CDCl₃, rt): δ 7.85 (d, 3JHH = 8.1 Hz, 2 H; Ar), 7.27 (d, 3JHH = 8.1 Hz, 2 H; Ar), 5.30 (dq, 2JHF = 47.6 Hz, 3JHH = 6.2 Hz, 1 H; CHFCH3), 3.48 (m, 1 H; CHH), 3.06 (m, 1 H; CHH), 2.41 (s, 3 H, C6H4CH3), 1.46 (dd, 3JHF = 24.1 Hz, 3JHH = 6.2 Hz, 3 H; CHFCH3); ¹³C NMR (126 MHz, CDCl₃, rt): δ 196.5 (d, 3JCF = 6.7 Hz), 144.3, 134.4, 129.4 (2 C), 128.3 (2 C), 87.3 (d, 1JCF = 165.4 Hz), 45.3 (d, 2JCF = 22.8 Hz), 21.7, 21.2 (d, 2JCF = 22.4 Hz); ¹⁹F NMR (376 MHz, CDCl₃, rt): δ -172.5 (m, 1 F); HRMS (ESI-TOF) calcd m/z for [C11H13FO+Na]⁺ 203.0843, found 203.0846. ¹ H NMR (400 MHz, CDCl ₃ , rt): δ 7.85 (d, 3JHH = 8.1 Hz, 2 H; Ar), 7.27 (d, 3JHH = 8.1 Hz, 2 H; Ar), 5.30 (dq, 2JHF = 47.6 Hz, 3JHH = 6.2 Hz, 1 H; CHFCH3), 3.48 (m, 1 H; CHH), 3.06 (m, 1 H; CHH), 2.41 (s, 3 H, C6H4CH3), 1.46 (dd, 3JHF = 24.1 Hz, 3JHH = 6.2 Hz, 3 H; CHFCH3); ¹³ C NMR (126 MHz, CDCl ₃ , rt): δ 196.5 (d, 3JCF = 6.7 Hz), 144.3, 134.4, 129.4 (2 C), 128.3 ( 2 C), 87.3 (d, 1JCF = 165.4 Hz), 45.3 (d, 2JCF = 22.8 Hz), 21.7, 21.2 (d, 2JCF = 22.4 Hz); ¹⁹ F NMR (376 MHz, CDCl ₃ , rt): δ -172.5 (m, 1 F); HRMS (ESI-TOF) calcd m / z for [C11H13FO + Na] ⁺ 203.0843, found 203.0846.

¹H NMR (400 MHz, CDCl₃, rt): δ 7.98 (dd, 3JHH = 8.7 Hz, 4JHF = 5.5 Hz, 2 H; Ar), 7.14 (dd, 3JHH = 8.7 Hz, 3JHF = 8.7 Hz, 2 H; Ar), 5.29 (dq, 2JHF = 47.6 Hz, 3JHH = 6.2 Hz, 1 H; CHF), 3.47 (m, 1 H; CHH), 3.04 (m, 1 H; CHH), 1.47 (dd, 3JHF = 24.1 Hz, 3JHH = 6.2 Hz, 3 H; CH3); ¹³C NMR (126 MHz, CDCl₃, rt): δ 195.4 (d, 3JCF = 6.3 Hz), 166.1 (d, 1JCF = 255.3 Hz), 133.5, 131.0 (d, 3JCF = 9.4 Hz, 2 C), 115.9 (d, 2JCF = 21.9 Hz, 2 C), 87.3 (d, 1JCF = 165.8 Hz), 45.5 (d, 2JCF = 23.1 Hz), 21.3 (d, 2JCF = 22.3 Hz); ¹⁹F NMR (376 MHz, CDCl₃, rt): δ -104.7 (m, 1 F; C6H4F), -172.5 (m, 1 F; CHF); HRMS (ESI-TOF) calcd m/z for [C10H10F2O+Na]⁺ 207.0592, found 207.0593. ¹ H NMR (400 MHz, CDCl ₃ , rt): δ 7.98 (dd, 3JHH = 8.7 Hz, 4JHF = 5.5 Hz, 2 H; Ar), 7.14 (dd, 3JHH = 8.7 Hz, 3JHF = 8.7 Hz, 2 H Ar), 5.29 (dq, 2JHF = 47.6 Hz, 3JHH = 6.2 Hz, 1 H; CHF), 3.47 (m, 1 H; CHH), 3.04 (m, 1 H; CHH), 1.47 (dd, 3JHF = 24.1 Hz, 3JHH = 6.2 Hz, 3 H; CH3); ¹³ C NMR (126 MHz, CDCl ₃ , rt): δ 195.4 (d, 3JCF = 6.3 Hz), 166.1 (d, 1JCF = 255.3 Hz), 133.5, 131.0 (d, 3JCF = 9.4 Hz, 2 C), 115.9 (d, 2JCF = 21.9 Hz, 2 C), 87.3 (d, 1JCF = 165.8 Hz), 45.5 (d, 2JCF = 23.1 Hz), 21.3 (d, 2JCF = 22.3 Hz); ¹⁹ F NMR (376 MHz, CDCl ₃ , rt): δ -104.7 (m, 1 F; C6H4F), -172.5 (m, 1 F; CHF); HRMS (ESI-TOF) calcd m / z for [C10H10F2O + Na] ⁺ 207.0592, found 207.0593.

¹H NMR (400 MHz, CDCl₃, rt): δ 7.93 (d, 3JHH = 8.8 Hz, 2 H; Ar), 6.93 (d, 3JHH = 8.8 Hz, 2 H; Ar), 5.28 (dq, 2JHF = 47.6 Hz, 3JHH = 6.2 Hz, 1 H; CHFCH3), 3.86 (s, 3 H; OCH3), 3.45 (m, 1 H; CHH), 3.02 (m, 1 H; CHH), 1.45 (dd, 3JHF = 24.2 Hz, 3JHH = 6.2 Hz, 3 H; CHFCH3); ¹³C NMR (126 MHz, CDCl₃, rt): δ 195.4 (d, 3JCF = 6.6 Hz), 163.8, 130.5 (2 C), 130.0, 113.8 (2 C), 87.4 (d, 1JCF = 165.2 Hz), 55.5, 45.1 (d, 2JCF = 22.8 Hz), 21.2 (d, 2JCF = 22.4 Hz); ¹⁹F NMR (376 MHz, CDCl₃, rt): δ -172.4 (m, 1 F); HRMS (ESI-TOF) calcd m/z for [C11H13FO2+Na]⁺ 219.0792, found 219.0792. ¹ H NMR (400 MHz, CDCl ₃ , rt): δ 7.93 (d, 3JHH = 8.8 Hz, 2 H; Ar), 6.93 (d, 3JHH = 8.8 Hz, 2 H; Ar), 5.28 (dq, 2JHF = 47.6 Hz, 3JHH = 6.2 Hz, 1 H; CHFCH3), 3.86 (s, 3 H; OCH3), 3.45 (m, 1 H; CHH), 3.02 (m, 1 H; CHH), 1.45 (dd, 3JHF = 24.2 Hz, 3JHH = 6.2 Hz, 3 H; CHFCH3); ¹³ C NMR (126 MHz, CDCl ₃ , rt): δ 195.4 (d, 3JCF = 6.6 Hz), 163.8, 130.5 (2 C), 130.0, 113.8 ( 2 C), 87.4 (d, 1JCF = 165.2 Hz), 55.5, 45.1 (d, 2JCF = 22.8 Hz), 21.2 (d, 2JCF = 22.4 Hz); ¹⁹ F NMR (376 MHz, CDCl ₃ , rt): δ -172.4 (m, 1 F); HRMS (ESI-TOF) calcd m / z for [C11H13FO2 + Na] ⁺ 219.0792, found 219.0792.

¹H NMR (400 MHz, CDCl₃, rt): δ 7.96 (d, 3JHH = 7.5 Hz, 2 H; Ar), 7.58 (t, 3JHH = 7.5 Hz, 1 H; Ar), 7.47 (t, 3JHH = 7.5 Hz, 2 H; Ar), 5.31 (dq, 2JHF = 47.5 Hz, 3JHH = 6.2 Hz, 1 H; CHF), 3.51 (m, 1 H; CHH), 3.09 (m, 1 H; CHH), 1.47 (dd, 3JHF = 24.2 Hz, 3JHH = 6.2 Hz, 3 H; CH3); ¹³C NMR (126 MHz, CDCl₃, rt): δ 197.0 (d, 3JCF = 6.7 Hz), 136.9, 133.5, 128.8 (2 C), 128.3 (2 C), 87.3 (d, 1JCF = 165.3 Hz), 45.5 (d, 2JCF = 23.0 Hz), 21.3 (d, 2JCF = 22.1 Hz); ¹⁹F NMR (376 MHz, CDCl₃, rt): δ -172.6 (m, 1 F); HRMS (ESI-TOF) calcd m/z for [C10H11FO+Na]⁺ 189.0686, found 189.0687. ¹ H NMR (400 MHz, CDCl ₃ , rt): δ 7.96 (d, 3JHH = 7.5 Hz, 2 H; Ar), 7.58 (t, 3JHH = 7.5 Hz, 1 H; Ar), 7.47 (t, 3JHH = 7.5 Hz, 2 H; Ar), 5.31 (dq, 2JHF = 47.5 Hz, 3JHH = 6.2 Hz, 1 H; CHF), 3.51 (m, 1 H; CHH), 3.09 (m, 1 H; CHH), 1.47 (dd, 3JHF = 24.2 Hz, 3JHH = 6.2 Hz, 3 H; CH3); ¹³ C NMR (126 MHz, CDCl ₃ , rt): δ 197.0 (d, 3JCF = 6.7 Hz), 136.9, 133.5, 128.8 (2) C), 128.3 (2 C), 87.3 (d, 1JCF = 165.3 Hz), 45.5 (d, 2JCF = 23.0 Hz), 21.3 (d, 2JCF = 22.1 Hz); ¹⁹ F NMR (376 MHz, CDCl ₃ , rt) ): δ -172.6 (m, 1 F); HRMS (ESI-TOF) calcd m / z for [C10H11FO + Na] ⁺ 189.0686, found 189.0687.

¹H NMR (400 MHz, CDCl₃, rt): δ 7.89 (d, 3JHH = 8.6 Hz, 2 H; Ar), 7.44 (d, 3JHH = 8.6 Hz, 2 H; Ar), 5.28 (dq, 2JHF = 47.5 Hz, 3JHH = 6.2 Hz, 1 H; CHF), 3.46 (m, 1 H; CHH), 3.04 (m, 1 H; CHH), 1.47 (dd, 3JHF = 24.1 Hz, 3JHH = 6.2 Hz, 3 H; CH3); ¹³C NMR (126 MHz, CDCl₃, rt): δ 195.8 (d, 3JCF = 6.0 Hz), 140.1, 135.2, 129.7 (2 C), 129.1 (2 C), 87.2 (d, 1JCF = 165.8 Hz), 45.4 (d, 2JCF = 23.2 Hz), 21.3 (d, 2JCF = 22.1 Hz); ¹⁹F NMR (376 MHz, CDCl₃, rt): δ -172.5 (m, 1 F); HRMS (ESI-TOF) calcd m/z for [C10H10ClFO+Na]⁺ 223.0296, found 223.0298. ¹ H NMR (400 MHz, CDCl ₃ , rt): δ 7.89 (d, 3JHH = 8.6 Hz, 2 H; Ar), 7.44 (d, 3JHH = 8.6 Hz, 2 H; Ar), 5.28 (dq, 2JHF = 47.5 Hz, 3JHH = 6.2 Hz, 1 H; CHF), 3.46 (m, 1 H; CHH), 3.04 (m, 1 H; CHH), 1.47 (dd, 3JHF = 24.1 Hz, 3JHH = 6.2 Hz, 3 H CH3); ¹³ C NMR (126 MHz, CDCl ₃ , rt): δ 195.8 (d, 3JCF = 6.0 Hz), 140.1, 135.2, 129.7 (2 C), 129.1 (2 C), 87.2 (d, 1JCF = 165.8 Hz), 45.4 (d, 2JCF = 23.2 Hz), 21.3 (d, 2JCF = 22.1 Hz); ¹⁹ F NMR (376 MHz, CDCl ₃ , rt): δ -172.5 (m, 1 F); HRMS (ESI) -TOF) calcd m / z for [C10H10ClFO + Na] ⁺ 223.0296, found 223.0298.

¹H NMR (400 MHz, CDCl₃, rt): δ 7.76 - 7.74 (2 H; Ar), 7.40 - 7.34 (2 H; Ar), 5.30 (dq, 2JHF = 47.5 Hz, 3JHH = 6.2 Hz, 1 H; CHFCH3), 3.49 (m, 1 H; CHH), 3.07 (m, 1 H; CHH), 2.41 (s, 3 H, C6H4CH3), 1.47 (dd, 3JHF = 24.1 Hz, 3JHH = 6.2 Hz, 3 H; CHFCH3); ¹³C NMR (126 MHz, CDCl₃, rt): δ 197.2 (d, 3JCF = 6.7 Hz), 138.6, 137.0, 134.3, 128.8, 128.7, 125.5, 87.4 (d, 1JCF = 165.5 Hz), 45.5 (d, 2JCF = 22.9 Hz), 21.5, 21.3 (d, 2JCF = 22.3 Hz); ¹⁹F NMR (376 MHz, CDCl₃, rt): δ -172.6 (m, 1 F); HRMS (ESI-TOF) calcd m/z for [C11H13FO+Na]⁺ 203.0843, found 203.0843. ^{1 1} H NMR (400 MHz, CDCl ₃ , rt): δ 7.76 --7.74 (2 H; Ar), 7.40 --7.34 (2 H; Ar), 5.30 (dq, 2JHF = 47.5 Hz, 3JHH = 6.2 Hz, 1 H CHFCH3), 3.49 (m, 1 H; CHH), 3.07 (m, 1 H; CHH), 2.41 (s, 3 H, C6H4CH3), 1.47 (dd, 3JHF = 24.1 Hz, 3JHH = 6.2 Hz, 3 H CHFCH3); ¹³ C NMR (126 MHz, CDCl ₃ , rt): δ 197.2 (d, 3JCF = 6.7 Hz), 138.6, 137.0, 134.3, 128.8, 128.7, 125.5, 87.4 (d, 1JCF = 165.5 Hz), 45.5 (d, 2JCF = 22.9 Hz), 21.5, 21.3 (d, 2JCF = 22.3 Hz); ¹⁹ F NMR (376 MHz, CDCl ₃ , rt): δ -172.6 (m, 1 F); HRMS (ESI-TOF) ) calcd m / z for [C11H13FO + Na] ⁺ 203.0843, found 203.0843.

¹H NMR (400 MHz, CDCl₃, rt): δ 8.14 (d, 3JHH = 8.4 Hz, 2 H; Ar), 8.01 (d, 3JHH = 8.4 Hz, 2 H; Ar), 5.31 (dq, 2JHF = 47.5 Hz, 3JHH = 6.1 Hz, 1 H; CHFCH3), 3.96 (s, 3 H, COOCH3), 3.53 (m, 1 H; CHH), 3.10 (m, 1 H; CHH), 1.49 (dd, 3JHF = 24.1 Hz, 3JHH = 6.1 Hz, 3 H; CHFCH3); ¹³C NMR (126 MHz, CDCl₃, rt): δ 196.5 (d, 3JCF = 6.0 Hz), 166.2, 140.0, 134.3, 130.0 (2 C), 128.2 (2 C), 87.1 (d, 1JCF = 165.9 Hz), 52.6, 45.8 (d, 2JCF = 23.0 Hz), 21.3 (d, 2JCF = 22.4 Hz); ¹⁹F NMR (376 MHz, CDCl₃, rt): δ -172.6 (m, 1 F); HRMS (ESI-TOF) calcd m/z for [C12H13FO3+Na]⁺ 247.0741, found 247.0738. ¹ H NMR (400 MHz, CDCl ₃ , rt): δ 8.14 (d, 3JHH = 8.4 Hz, 2 H; Ar), 8.01 (d, 3JHH = 8.4 Hz, 2 H; Ar), 5.31 (dq, 2JHF = 47.5 Hz, 3JHH = 6.1 Hz, 1 H; CHFCH3), 3.96 (s, 3 H, COOCH3), 3.53 (m, 1 H; CHH), 3.10 (m, 1 H; CHH), 1.49 (dd, 3JHF = 24.1 Hz, 3JHH = 6.1 Hz, 3 H; CHFCH3); ¹³ C NMR (126 MHz, CDCl ₃ , rt): δ 196.5 (d, 3JCF = 6.0 Hz), 166.2, 140.0, 134.3, 130.0 (2 C), 128.2 (2 C), 87.1 (d, 1JCF = 165.9 Hz), 52.6, 45.8 (d, 2JCF = 23.0 Hz), 21.3 (d, 2JCF = 22.4 Hz); ¹⁹ F NMR (376 MHz, CDCl ₃ , rt) : δ -172.6 (m, 1 F); HRMS (ESI-TOF) calcd m / z for [C12H13FO3 + Na] ⁺ 247.0741, found 247.0738.

¹H NMR (400 MHz, CDCl₃, rt): δ 7.82 (d, 3JHH = 8.5 Hz, 2 H; Ar), 7.62 (d, 3JHH = 8.5 Hz, 2 H; Ar), 5.29 (dq, 2JHF = 47.4 Hz, 3JHH = 6.2 Hz, 1 H; CHFCH3), 3.46 (m, 1 H; CHH), 3.04 (m, 1 H; CHH), 1.47 (dd, 3JHF = 24.1 Hz, 3JHH = 6.2 Hz, 3 H; CHFCH3); ¹³C NMR (126 MHz, CDCl₃, rt): δ 196.0 (d, 3JCF = 6.1 Hz), 135.6, 132.1 (2 C), 129.8 (2 C), 128.8, 87.2 (d, 1JCF = 165.8 Hz), 45.4 (d, 2JCF = 23.1 Hz), 21.3 (d, 2JCF = 22.1 Hz); ¹⁹F NMR (376 MHz, CDCl₃, rt): δ -172.6 (m, 1 F); HRMS (ESI-TOF) calcd m/z for [C10H10BrFO+Na]⁺ 266.9791, found 266.9789. ¹ H NMR (400 MHz, CDCl ₃ , rt): δ 7.82 (d, 3JHH = 8.5 Hz, 2 H; Ar), 7.62 (d, 3JHH = 8.5 Hz, 2 H; Ar), 5.29 (dq, 2JHF = 47.4 Hz, 3JHH = 6.2 Hz, 1 H; CHFCH3), 3.46 (m, 1 H; CHH), 3.04 (m, 1 H; CHH), 1.47 (dd, 3JHF = 24.1 Hz, 3JHH = 6.2 Hz, 3 H CHFCH3); ¹³ C NMR (126 MHz, CDCl ₃ , rt): δ 196.0 (d, 3JCF = 6.1 Hz), 135.6, 132.1 (2 C), 129.8 (2 C), 128.8, 87.2 (d, 1JCF = 165.8 Hz), 45.4 (d, 2JCF = 23.1 Hz), 21.3 (d, 2JCF = 22.1 Hz); ¹⁹ F NMR (376 MHz, CDCl ₃ , rt): δ -172.6 (m, 1 F); HRMS (ESI) -TOF) calcd m / z for [C10H10BrFO + Na] ⁺ 266.9791, found 266.9789.

¹H NMR (400 MHz, CDCl₃, rt): δ 7.74 (dd, 3JHH = 3.9 Hz, 4JHH = 0.7 Hz, 1 H; Ar), 7.67 (dd, 3JHH = 4.8 Hz, 4JHH = 0.7 Hz, 1 H; Ar), 7.15 (dd, 3JHH = 4.8, 3.9 Hz, 1 H; Ar), 5.27 (dq, 2JHF = 47.6 Hz, 3JHH = 6.2 Hz, 1 H; CHFCH3), 3.42 (m, 1 H; CHH), 3.02 (m, 1 H; CHH), 1.47 (dd, 3JHF = 24.0 Hz, 3JHH = 6.2 Hz, 3 H; CHFCH3); ¹³C NMR (126 MHz, CDCl₃, rt): δ 189.7 (d, 3JCF = 6.5 Hz), 144.4 (d, 4JCF = 1.3 Hz), 134.5, 132.7, 128.4, 87.3 (d, 1JCF = 166.7 Hz), 46.3 (d, 2JCF = 23.2 Hz), 21.3 (d, 2JCF = 22.4 Hz); ¹⁹F NMR (376 MHz, CDCl₃, rt): δ -172.0 (m, 1 F); HRMS (ESI-TOF) calcd m/z for [C8H9FOS+Na]⁺ 195.0250, found 195.0248. ¹ H NMR (400 MHz, CDCl ₃ , rt): δ 7.74 (dd, 3JHH = 3.9 Hz, 4JHH = 0.7 Hz, 1 H; Ar), 7.67 (dd, 3JHH = 4.8 Hz, 4JHH = 0.7 Hz, 1 H Ar), 7.15 (dd, 3JHH = 4.8, 3.9 Hz, 1 H; Ar), 5.27 (dq, 2JHF = 47.6 Hz, 3JHH = 6.2 Hz, 1 H; CHFCH3), 3.42 (m, 1 H; CHH) , 3.02 (m, 1 H; CHH), 1.47 (dd, 3JHF = 24.0 Hz, 3JHH = 6.2 Hz, 3 H; CHFCH3); ¹³ C NMR (126 MHz, CDCl ₃ , rt): δ 189.7 (d, 3JCF) = 6.5 Hz), 144.4 (d, 4JCF = 1.3 Hz), 134.5, 132.7, 128.4, 87.3 (d, 1JCF = 166.7 Hz), 46.3 (d, 2JCF = 23.2 Hz), 21.3 (d, 2JCF = 22.4 Hz) ¹⁹ F NMR (376 MHz, CDCl ₃ , rt): δ -172.0 (m, 1 F); HRMS (ESI-TOF) calcd m / z for [C8H9FOS + Na] ⁺ 195.0250, found 195.0248.

¹H NMR (400 MHz, CDCl₃, rt): δ 8.33 (d, 3JHH = 8.8 Hz, 2 H; Ar), 8.11 (d, 3JHH = 8.8 Hz, 2 H; Ar), 5.31 (dq, 2JHF = 47.5 Hz, 3JHH = 6.2 Hz, 1 H; CHFCH3), 3.53 (m, 1 H; CHH), 3.11 (m, 1 H; CHH), 1.50 (dd, 3JHF = 24.2 Hz, 3JHH = 6.2 Hz, 3 H; CHFCH3); ¹³C NMR (126 MHz, CDCl₃, rt): δ 195.6 (d, 3JCF = 5.8 Hz), 150.6, 141.3, 129.4 (2 C), 124.1 (2 C), 87.0 (d, 1JCF = 166.5 Hz), 46.0 (d, 2JCF = 23.4 Hz), 21.2 (d, 2JCF = 22.3 Hz); ¹⁹F NMR (376 MHz, CDCl₃, rt): δ -172.5 (m, 1 F); HRMS (ESI-TOF) calcd m/z for [C10H10FNO3+Na]⁺ 234.0537, found 234.0535. ¹ H NMR (400 MHz, CDCl ₃ , rt): δ 8.33 (d, 3JHH = 8.8 Hz, 2 H; Ar), 8.11 (d, 3JHH = 8.8 Hz, 2 H; Ar), 5.31 (dq, 2JHF = 47.5 Hz, 3JHH = 6.2 Hz, 1 H; CHFCH3), 3.53 (m, 1 H; CHH), 3.11 (m, 1 H; CHH), 1.50 (dd, 3JHF = 24.2 Hz, 3JHH = 6.2 Hz, 3 H CHFCH3); ¹³ C NMR (126 MHz, CDCl ₃ , rt): δ 195.6 (d, 3JCF = 5.8 Hz), 150.6, 141.3, 129.4 (2 C), 124.1 (2 C), 87.0 (d, 1JCF = 166.5 Hz), 46.0 (d, 2JCF = 23.4 Hz), 21.2 (d, 2JCF = 22.3 Hz); ¹⁹ F NMR (376 MHz, CDCl ₃ , rt): δ -172.5 (m, 1 F); HRMS (ESI) -TOF) calcd m / z for [C10H10FNO3 + Na] ⁺ 234.0537, found 234.0535.

¹H NMR (400 MHz, CDCl₃, rt): δ 8.05 (d, 3JHH = 8.4 Hz, 2 H; Ar), 7.79 (d, 3JHH = 8.4 Hz, 2 H; Ar), 5.30 (dq, 2JHF = 47.4 Hz, 3JHH = 6.1 Hz, 1 H; CHFCH3), 3.50 (m, 1 H; CHH), 3.08 (m, 1 H; CHH), 1.49 (dd, 3JHF = 24.0 Hz, 3JHH = 6.1 Hz, 3 H; CHFCH3); ¹³C NMR (126 MHz, CDCl₃, rt): δ 195.8 (d, 3JCF = 5.8 Hz), 139.8, 132.7 (2 C), 128.7 (2 C), 117.9, 116.8, 87.0 (d, 1JCF = 166.3 Hz), 45.7 (d, 2JCF = 23.0 Hz), 21.2 (d, 2JCF = 22.5 Hz); ¹⁹F NMR (376 MHz, CDCl₃, rt): δ -172.5 (m, 1 F); HRMS (ESI-TOF) calcd m/z for [C11H10FNO+Na]⁺ 214.0639, found 214.0640. ¹ H NMR (400 MHz, CDCl ₃ , rt): δ 8.05 (d, 3JHH = 8.4 Hz, 2 H; Ar), 7.79 (d, 3JHH = 8.4 Hz, 2 H; Ar), 5.30 (dq, 2JHF = 47.4 Hz, 3JHH = 6.1 Hz, 1 H; CHFCH3), 3.50 (m, 1 H; CHH), 3.08 (m, 1 H; CHH), 1.49 (dd, 3JHF = 24.0 Hz, 3JHH = 6.1 Hz, 3 H CHFCH3); ¹³ C NMR (126 MHz, CDCl ₃ , rt): δ 195.8 (d, 3JCF = 5.8 Hz), 139.8, 132.7 (2 C), 128.7 (2 C), 117.9, 116.8, 87.0 (d, 1JCF = 166.3 Hz), 45.7 (d, 2JCF = 23.0 Hz), 21.2 (d, 2JCF = 22.5 Hz); ¹⁹ F NMR (376 MHz, CDCl ₃ , rt): δ -172.5 (m, 1 F); HRMS (ESI-TOF) calcd m / z for [C11H10FNO + Na] ⁺ 214.0639, found 214.0640.

〔実施例５〕クロロベンゼン類の脱塩素化反応
窒素雰囲気下で、NMRチューブに、メチル-4-クロロベンゾエート (7.70 mg, 0.0451 mmol)、BDB (0.92 mg, 2.20 μmol)、トリブチルアミン (48.3 mg, 0.261 mmol)、HCOOH (5.7 mg, 0.124 mmol)、CD₃CN (0.5 mL)、内部標準としてテトラエチルシラン (2 μL)を加えた。この混合物を凍結脱気後、水浴内で2〜3 cm離した位置からLEDランプ（λ= 380 nm）を照射した。光照射2時間後には、脱塩素化体が収率80％で生成した。 [Example 5] Dechlorination reaction of chlorobenzenes
Methyl-4-chlorobenzoate (7.70 mg, 0.0451 mmol), BDB (0.92 mg, 2.20 μmol), tributylamine (48.3 mg, 0.261 mmol), HCOOH (5.7 mg, 0.124 mmol) in an NMR tube under a nitrogen atmosphere. , CD ₃ CN (0.5 mL), tetraethylsilane (2 μL) as an internal standard. After freezing and degassing this mixture, the LED lamp (λ = 380 nm) was irradiated from a position 2 to 3 cm away in the water bath. Two hours after light irradiation, a dechlorinated product was produced in a yield of 80%.

〔実施例６〕触媒活性の比較
アルケンのヒドロキシ-モノフルオロメチル化をプローブにして触媒の活性を比較した。
スルホキシミン型のCH₂F試薬は非常に還元されにくい試薬（E_red=-2.43 V）である。1.5当量のCH₂F試薬、p-ビニルビフェニル、5 mol%のBDNのアセトン-d₆/D₂O混合物に可視光照射（λ= 425 nm）すると、期待されるモノフルオロメチル化生成物が得られた（図２）。いくつかの強い還元力を持つ光触媒を同条件で検討した。例えばfac-[Ir(ppy)₃]、フェノチアジン、5,10-ジヒドロフェナジン誘導体、ペリレンはBDNよりも活性が低いことがわかった（図２）。BDNの高い触媒性能は、より強い還元力だけでなく、可視光吸収能力、およびその堅牢性に起因すると考えられる。 [Example 6] Comparison of catalytic activity The activity of the catalyst was compared using hydroxy-monofluoromethylation of alkene as a probe.
The sulfoximine type CH ₂ F reagent is a reagent that is extremely difficult to reduce (E _red = -2.43 V). Visible light irradiation (λ = 425 nm) of 1.5 equivalents of CH ₂ F reagent, p-vinylbiphenyl, 5 mol% BDN acetone-d ₆ / D _{2 O mixture yields the expected monofluoromethylation product.} Obtained (Fig. 2). Several photocatalysts with strong reducing power were examined under the same conditions. For example, fac- [Ir (ppy) ₃ ], phenothiazine, 5,10-dihydrophenazine derivative, and perylene were found to be less active than BDN (Fig. 2). The high catalytic performance of BDN is considered to be due to its ability to absorb visible light and its robustness as well as its stronger reducing power.

本発明により、医薬や農薬として有用な有機フッ素化合物を効率的に合成できるようになるので、本発明は、医薬や農薬に関連する産業分野において利用可能である。 Since the present invention enables efficient synthesis of organofluorine compounds useful as pharmaceuticals and pesticides, the present invention can be used in industrial fields related to pharmaceuticals and pesticides.

Claims

The following general formula (I) or general formula (II)
[In the formula, Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ , Ar ⁷ , and Ar ⁸ are each independently substituted with an aryl group or a substituent which may be substituted with a substituent. Represents a heteroaryl group that may be, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ are independent hydrogen atoms, respectively. Represents a halogen atom, an aryl group optionally substituted with a substituent, or a heteroaryl group optionally substituted with a substituent. ]
A photoredox catalyst comprising a compound represented by.

^{Ar 1} , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ , Ar ⁷ , and Ar ⁸ in the compounds represented by the general formulas (I) and (II) are independently substituents. The photoredox catalyst according to claim 1, wherein the photoredox catalyst is a phenyl group which may be substituted.

^{Ar 1} , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ , Ar ⁷ , and Ar ⁸ in the compounds represented by the general formulas (I) and (II) are independently phenyl groups or The photoredox catalyst according to claim 1, wherein the 4-position, 3-position, or 2-position is a phenyl group substituted with a substituent.

^{Ar 1} , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ , Ar ⁷ , and Ar ⁸ in the compounds represented by the general formulas (I) and (II) are independently phenyl groups, respectively. The photoredox catalyst according to claim 1, wherein the photoredox catalyst is a 4-tert-butylphenyl group or a 4-fluorophenyl group.

^{R 1} , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ in the compounds represented by the general formulas (I) and (II) are hydrogen. The photoredox catalyst according to any one of claims 1 to 4, which is an atom.

A method for producing a compound, which comprises activating an organic compound by a redox reaction in the presence of the photoredox catalyst according to any one of claims 1 to 5 under light irradiation.

The redox reaction is catalyzed by fac-tris (2-phenylpyridine) iridium (III) or tris (2,2'-bipyridine) ruthenium (II) bis (hexafluorophosphate). The method for producing a compound according to claim 6, which is characterized.

The method for producing a compound according to claim 6, wherein the redox reaction is a hydroxy-monofluoromethylation reaction of an aromatic alkene or a monofluoroalkylation reaction of an aromatic vinyl acetate.

The compound according to claim 6, wherein the photoredox catalyst is a photoredox catalyst containing a compound represented by the general formula (II), and the redox reaction is a dechlorination reaction of chlorobenzenes. Production method.