JP5021248B2 - Method for producing optically active compound - Google Patents

Method for producing optically active compound Download PDF

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JP5021248B2
JP5021248B2 JP2006196477A JP2006196477A JP5021248B2 JP 5021248 B2 JP5021248 B2 JP 5021248B2 JP 2006196477 A JP2006196477 A JP 2006196477A JP 2006196477 A JP2006196477 A JP 2006196477A JP 5021248 B2 JP5021248 B2 JP 5021248B2
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hexane
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憲夫 宮浦
靖典 山本
孝司 西形
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Hokkaido University NUC
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Description

この発明は、光学活性β-ジアリールカルボニル化合物からなる光学活性化合物の製造方法に関する。 The present invention relates to a method for producing an optically active compound comprising an optically active β-diarylcarbonyl compound.

光学活性β‐ジアリールカルボニル化合物は、医農薬分野等で中間体として有用な化合物である。例えば、光学活性β‐ジアリールカルボニル化合物の分子内環化体であるクロマノール誘導体から、天然生物活性物質である4H-クロメンを容易に合成することができる。 The optically active β-diarylcarbonyl compound is a useful compound as an intermediate in the field of medicine and agrochemicals. For example, 4H-chromene, which is a natural biologically active substance, can be easily synthesized from a chromanol derivative which is an intramolecular cyclized product of an optically active β-diarylcarbonyl compound.

従来、β−ジアリールカルボニル化合物の製造方法として、ロジウム触媒の存在下、アリール金属反応剤とα,β−不飽和カルボニル化合物を反応させる方法が報告されている（非特許文献１）。しかし、この方法では光学活性化合物は合成されていない。又、光学活性β−ジアリールカルボニル化合物の製造方法として、ロジウム化合物に光学活性ホスホロアミダイト化合物を加えたロジウム触媒の存在下、アリール金属反応剤をα,β−不飽和エノンと反応させて製造する方法が報告されている（非特許文献２、３）。しかし、この方法の場合、収率、選択性共に実用的ではない。 一方、クロメン類の製造法として、パラジウム触媒を用い、アリール水銀化合物をα,β-不飽和ケトンへ共役付加させる方法が知られている（非特許文献４）。しかし、この方法は、水銀化合物を使用する点で好ましくなく、又、光学活性クロメン類の合成はなされていない。 Conventionally, as a method for producing a β-diarylcarbonyl compound, a method of reacting an aryl metal reactant with an α, β-unsaturated carbonyl compound in the presence of a rhodium catalyst has been reported (Non-patent Document 1). However, no optically active compound is synthesized by this method. In addition, as an optically active β-diarylcarbonyl compound production method, an aryl metal reactant is reacted with an α, β-unsaturated enone in the presence of a rhodium catalyst obtained by adding an optically active phosphoramidite compound to a rhodium compound. Methods have been reported (Non-Patent Documents 2 and 3). However, this method is not practical in terms of yield and selectivity. On the other hand, as a method for producing chromenes, a method of conjugate addition of an arylmercury compound to an α, β-unsaturated ketone using a palladium catalyst is known (Non-patent Document 4). However, this method is not preferable in that a mercury compound is used, and optically active chromenes have not been synthesized.

ところで本発明者らは、β‐ジアリールカルボニル化合物の製造法ではないが、パラジウム錯体触媒を用いて電子吸引性基置換化合物（マイケル付加物）を製造する方法を報告している（特許文献１）。 By the way, the present inventors have reported a method for producing an electron-withdrawing group-substituted compound (Michael adduct) using a palladium complex catalyst, although it is not a method for producing a β-diarylcarbonyl compound (Patent Document 1). .

特開2004-315457号公報JP 2004-315457 A S. Oi, M. Moro, H. Ito, Y. Honma, S. Miyano, Y. Inoue, Tetrahedron 2002, 58, 91.S. Oi, M. Moro, H. Ito, Y. Honma, S. Miyano, Y. Inoue, Tetrahedron 2002, 58, 91. J.-G. Boiteau, R. Imbos, A. J. Minnaard, B. L. Feringa, Organic Letters 2003, 5, 681.J.-G. Boiteau, R. Imbos, A. J. Minnaard, B. L. Feringa, Organic Letters 2003, 5, 681. A. Duursma, R. Hoen, J. Schuppan, R. Hulst, A. J. Minnaard, B. L. Feringa, Organic Letters 2003, 5, 3111.A. Duursma, R. Hoen, J. Schuppan, R. Hulst, A. J. Minnaard, B. L. Feringa, Organic Letters 2003, 5, 3111. S. Cacchi, D. Misiti, G. Palmieri, J. Org. Chem. 1982, 47, 2995.S. Cacchi, D. Misiti, G. Palmieri, J. Org. Chem. 1982, 47, 2995.

本発明者らは、光学活性β-ジアリールカルボニル化合物を高収率、高選択性で製造する方法について鋭意検討した結果、上記特許文献１記載の技術において、パラジウム触媒として特定のものを用いることを見出した。 すなわち、本発明は、光学活性β-ジアリールカルボニル化合物を高収率、高選択性で製造できる方法の提供を目的とする。 As a result of intensive studies on a method for producing an optically active β-diarylcarbonyl compound with high yield and high selectivity, the inventors of the present invention have decided to use a specific palladium catalyst in the technique described in Patent Document 1. I found it. That is, an object of the present invention is to provide a method capable of producing an optically active β-diarylcarbonyl compound with high yield and high selectivity.

又、本発明の光学活性化合物の製造方法は、一般式（VI）
（式VI中、R１,R２はそれぞれ同一又は異なっていても良い水素又はアルキル基を表し、R3は水素、アルキル基、又は置換若しくは無置換のアリール基を表し、R4は塩素原子、フッ素原子、ヒドロキシ基、炭素数１から８のアルキル基、炭素数１から８のアルキル基を有していてもよいフェニル基、炭素数２から８のアルケニル基、炭素数２から８のアルキニル基、炭素数１から８のアルコキシ基、炭素数１から８のアルキルチオ基、シアノ基、ホルミル基、炭素数２から８のアシル基、炭素数１から８のアルキル基を有していてもよいベンゾイル基、炭素数２から８のアルコキシカルボニル基、炭素数１から８のアルキル基を有していてもよいフェノキシカルボニル基、炭素数１から８のアルキル基を有していてもよいアミノ基、炭素数１から８のアルキル基を有していてもよいカルバモイル基、ニトロ基、炭素数１から８のフルオロアルキル基、又は炭素数１から８のアルキル基を有していてもよいフェノキシ基を表す。）で表されるα,β-不飽和-β-アリールカルボニル化合物と、一般式（II）Ar2-BXmMnで表されるアリールボロン酸若しくはその誘導体、又は一般式（III）
（式II及びIII中、Ar２は置換または無置換のアリール基を表し、Xは水酸基、アルコキシ基、又はフッ素原子を示し、mは1から3の整数であり、Mはアルカリ金属であり、nは０または１の整数である。）で表されるアリールボロン酸無水物とを、一般式（IV）PdYoL1 p(Chiraphos)q(式IV中、YはClO4、BF4、PF6、SbF6、OTf、ハロゲン原子、ヒドロキシ基、アルコキシ基、アシルオキシ基を表し、L１は有機配位子、L２は光学活性ホスフィン配位子を示す。o,p,qはそれぞれ０から６の整数を表す。)で表されるパラジウム錯体触媒の存在下で反応させ、一般式（VII）
(式VII中、Ar１、Ar2、R1,R2,R3及びR4はそれぞれ式II〜Vに用いた置換基と同一である)で表されるクロマノール誘導体（VII）を製造することを特徴とする。 In addition, the process for producing the optically active compound of the present invention comprises the general formula (VI)
(In Formula VI, R 1 and R 2 each represent hydrogen or an alkyl group which may be the same or different, R 3 represents hydrogen, an alkyl group, or a substituted or unsubstituted aryl group, and R 4 represents a chlorine atom. , Fluorine atom, hydroxy group, alkyl group having 1 to 8 carbon atoms, phenyl group optionally having 1 to 8 carbon atoms, alkenyl group having 2 to 8 carbon atoms, alkynyl having 2 to 8 carbon atoms Group, an alkoxy group having 1 to 8 carbon atoms, an alkylthio group having 1 to 8 carbon atoms, a cyano group, a formyl group, an acyl group having 2 to 8 carbon atoms, and an alkyl group having 1 to 8 carbon atoms. A benzoyl group, an alkoxycarbonyl group having 2 to 8 carbon atoms, a phenoxycarbonyl group optionally having an alkyl group having 1 to 8 carbon atoms, an amino group optionally having an alkyl group having 1 to 8 carbon atoms, 1 carbon A carbamoyl group optionally having 8 alkyl groups, a nitro group, a fluoroalkyl group having 1 to 8 carbon atoms, or a phenoxy group optionally having an alkyl group having 1 to 8 carbon atoms. An α, β-unsaturated-β-arylcarbonyl compound represented by general formula (II), an arylboronic acid represented by Ar 2 -BX m Mn or a derivative thereof, or general formula (III)
(In formulas II and III, Ar 2 represents a substituted or unsubstituted aryl group, X represents a hydroxyl group, an alkoxy group, or a fluorine atom, m is an integer of 1 to 3, M is an alkali metal, n is an integer of 0 or 1.) An arylboronic acid anhydride represented by the general formula (IV) PdY o L 1 p (Chiraphos) q (wherein Y is ClO 4 , BF 4 , PF 6 , SbF 6 , OTf, halogen atom, hydroxy group, alkoxy group, acyloxy group, L 1 represents an organic ligand, L 2 represents an optically active phosphine ligand, and o, p, and q are 0, respectively. To 6 in the presence of a palladium complex catalyst represented by the general formula (VII)
(In formula VII, Ar 1 , Ar 2 , R 1 , R 2 , R 3 and R 4 are the same as the substituents used in formulas II to V, respectively) to produce a chromanol derivative (VII) It is characterized by that.

本発明において、反応系に銀塩を加えることが好ましい。 In the present invention, it is preferable to add a silver salt to the reaction system.

この発明によれば、光学活性β-ジアリールカルボニル化合物を高収率、高選択性で製造できる。 According to this invention, an optically active β-diarylcarbonyl compound can be produced with high yield and high selectivity.

本発明は、以下の１）α,β-不飽和-β-アリールカルボニル化合物、２）アリールボロン酸若しくはその誘導体、又はアリールボロン酸無水物、３）パラジウム錯体触媒、を反応させ、４）β-ジアリールカルボニル化合物を製造する方法である。 The present invention comprises reacting the following 1) α, β-unsaturated β-arylcarbonyl compound, 2) arylboronic acid or derivative thereof, or arylboronic acid anhydride, 3) palladium complex catalyst, 4) β A process for producing a diarylcarbonyl compound.

<α,β-不飽和-β-アリールカルボニル化合物> 基質であるα,β-不飽和-β-アリールカルボニル化合物は、一般式（I）
（式中Ar１は置換または無置換のアリール基を表し、R１,R２はそれぞれ同一又は異なっていても良い水素又はアルキル基を表し、Eはホルミル基又はアシル基を表す。）で表される。 <α, β-Unsaturated-β-Arylcarbonyl Compound> The substrate α, β-unsaturated-β-arylcarbonyl compound is represented by the general formula (I)
(Wherein Ar 1 represents a substituted or unsubstituted aryl group, R 1 and R 2 each independently represent a hydrogen atom or an alkyl group, and E represents a formyl group or an acyl group). Is done.

Ar１としては、フェニル基、ナフチル基、ピローリル基、チオフェニル基、フラニル基、インドーリル基、ベンゾフラニル基、及びピリジル基等の芳香環が挙げられる。これら芳香環の置換基としては塩素原子、フッ素原子、ヒドロキシ基、炭素数1から8のアルキル基、炭素数1から８のアルキル基を有していてもよいフェニル基、炭素数２から8のアルケニル基、炭素数2から8のアルキニル基、炭素数１から８のアルコキシ基、炭素数1から8のアルキルチオ基、シアノ基、ホルミル基、炭素数２から８のアシル基、炭素数1から8のアルキル基を有していてもよいベンゾイル基、炭素数２から８のアルコキシカルボニル基、炭素数1から8のアルキル基を有していてもよいフェノキシカルボニル基、炭素数１から８のアルキル基を有していてもよいアミノ基、炭素数１から８のアルキル基を有していてもよいカルバモイル基、ニトロ基、炭素数１から８のフルオロアルキル基、炭素数１から８のアルキル基を有していてもよいフェノキシ基，及びシクロへキシルオキシ基等が挙げられる。Ar１として具体的には、例えば、フェニル基、o-トリル基、ｍ-トリル基、ｐ-トリル基、o−メトキシフェニル基、m−メトキシフェニル基、p−メトキシフェニル基、p−トリフルオロメチルフェニル基、2−ナフチル基、（2-ベンジロキシ-5-メチル）フェニル基、(2-ヒドロキシ-5-メチル)フェニル基、及び(2-ヒドロキシ-5-メトキシ)フェニル基等が挙げられる。 Ar 1 includes aromatic rings such as a phenyl group, a naphthyl group, a pyrrolyl group, a thiophenyl group, a furanyl group, an indolyl group, a benzofuranyl group, and a pyridyl group. These aromatic ring substituents include chlorine atoms, fluorine atoms, hydroxy groups, alkyl groups having 1 to 8 carbon atoms, phenyl groups which may have an alkyl group having 1 to 8 carbon atoms, and those having 2 to 8 carbon atoms. Alkenyl group, C2-C8 alkynyl group, C1-C8 alkoxy group, C1-C8 alkylthio group, cyano group, formyl group, C2-C8 acyl group, C1-C8 A benzoyl group optionally having an alkyl group, an alkoxycarbonyl group having 2 to 8 carbon atoms, a phenoxycarbonyl group optionally having an alkyl group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms An amino group which may have an alkyl group, a carbamoyl group which may have an alkyl group having 1 to 8 carbon atoms, a nitro group, a fluoroalkyl group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms Have Good phenoxy group, and a hexyloxy group and the like cyclohexylene. Specific examples of Ar 1 include, for example, phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, o-methoxyphenyl group, m-methoxyphenyl group, p-methoxyphenyl group, p-trifluoro group. Examples thereof include a methylphenyl group, 2-naphthyl group, (2-benzyloxy-5-methyl) phenyl group, (2-hydroxy-5-methyl) phenyl group, and (2-hydroxy-5-methoxy) phenyl group.

R1,R2としては、水素又は炭素数1から8のアルキル基が挙げられ、アルキル基としては例えばメチル基、エチル基、n−プロキル基、イソプロピル基、n−ペンチル基、及びシクロへキシル基等が挙げられる。R1,R2として好ましくは水素を用いる。 Eとしてはホルミル基、又は炭素数２から８のアシル基が挙げられる。アシル基としては、例えばメチルカルボニル、エチルカルボニル、n-プロピルカルボニル、イソプロピルカルボニル、n-ブチルカルボニル、シクロへキシルカルボニルの他、炭素数１から８のアルキル基、炭素数１から８のアルコキシ基、ニトロ基、シアノ基、又は炭素数２から８のアルコキシカルボニル基等の置換基を芳香環上に１から５個有していてもよいアリールカルボニル基が挙げられる。 Examples of R 1 and R 2 include hydrogen or an alkyl group having 1 to 8 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-pentyl group, and a cyclohexyl group. Groups and the like. Hydrogen is preferably used as R 1 and R 2 . Examples of E include a formyl group or an acyl group having 2 to 8 carbon atoms. Examples of the acyl group include methylcarbonyl, ethylcarbonyl, n-propylcarbonyl, isopropylcarbonyl, n-butylcarbonyl, cyclohexylcarbonyl, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, Examples include an arylcarbonyl group which may have 1 to 5 substituents such as a nitro group, a cyano group, or an alkoxycarbonyl group having 2 to 8 carbon atoms on an aromatic ring.

上記一般式(I)で示される化合物の具体例としては、例えば、trans-4-フェニル-3-ブテン-2-オン、trans-カルコン、trans-1-フェニル-1-ヘプテン-3-オン、trans-4-メチル-1-fフェニル-1-ペンテン-3-オン、trans-1-シクロへキシル-3-フェニル-2-プロペン-1-オン、trans-1-(4-メトキシフェニル)-3-フェニル-2-プロペン-1-オン、trans-1-(4-ニトロフェニル)-3-フェニル-2-プロペン-1-オン、trans-3-(4-メトキシフェニル)-1-フェニル-2-プロペン-1-オン、trans-3-(2-ベンジロキシ-5-メチルフェニル)-1-フェニル-2-プロペン-1-オン、trans-4-(2-ベンジロキシ-5-メチルフェニル)-3-ブテン-2-オン、trans-4-(2-ヒドロキシ-5-メチルフェニル)-3-ブテン-2-オン、trans-4-(2-ヒドロキシ-5-メトキシフェニル)-3-ブテン-2-オン、trans-3-(2-ヒドロキシフェニル)-1-フェニル-2-プロペン-1-オン等が挙げられる。 Specific examples of the compound represented by the general formula (I) include, for example, trans-4-phenyl-3-buten-2-one, trans-chalcone, trans-1-phenyl-1-hepten-3-one, trans-4-methyl-1-fphenyl-1-penten-3-one, trans-1-cyclohexyl-3-phenyl-2-propen-1-one, trans-1- (4-methoxyphenyl)- 3-phenyl-2-propen-1-one, trans-1- (4-nitrophenyl) -3-phenyl-2-propen-1-one, trans-3- (4-methoxyphenyl) -1-phenyl- 2-propen-1-one, trans-3- (2-benzyloxy-5-methylphenyl) -1-phenyl-2-propen-1-one, trans-4- (2-benzyloxy-5-methylphenyl)- 3-buten-2-one, trans-4- (2-hydroxy-5-methylphenyl) -3-buten-2-one, trans-4- (2-hydroxy-5-methoxyphenyl) -3-butene- 2-one, trans-3- (2-hydroxyphenyl) -1-phenyl-2-propen-1-one, and the like.

<アリールボロン酸若しくはその誘導体、又はアリールボロン酸無水物> アリールボロン酸若しくはその誘導体、又はアリールボロン酸無水物は上記反応基質と不斉共役付加反応し、一般式（II）Ar2-BXmMn、又は一般式（III）
（式II及びIII中、Ar２は置換または無置換のアリール基を表し、Xは水酸基、アルコキシ基、又はフッ素原子を示し、mは1から3の整数であり、Mはアルカリ金属であり、nは０または１の整数である。）で表される。 <Arylboronic acid or derivative thereof, or arylboronic acid anhydride> Arylboronic acid or derivative thereof, or arylboronic acid anhydride undergoes an asymmetric conjugate addition reaction with the above reaction substrate, and is represented by the general formula (II) Ar 2 -BX m M n or general formula (III)
(In formulas II and III, Ar 2 represents a substituted or unsubstituted aryl group, X represents a hydroxyl group, an alkoxy group, or a fluorine atom, m is an integer of 1 to 3, M is an alkali metal, n is an integer of 0 or 1.)

Ar2としては、フェニル基、ナフチル基、ピローリル基、チオフェニル基、フラニル基、インドーリル基、ベンゾフラニル基、又はピリジル基等の芳香環が挙げられる。これら芳香環の置換基としては塩素原子、フッ素原子、炭素数1から8のアルキル基、炭素数1から８のアルキル基を有していてもよいフェニル基、炭素数２から8のアルケニル基、炭素数2から8のアルキニル基、炭素数１から８のアルコキシ基、炭素数1から8のアルキルチオ基、シアノ基、ホルミル基、炭素数２から８のアシル基、炭素数1から8のアルキル基を有していてもよいベンゾイル基、炭素数２から８のアルコキシカルボニル基、炭素数1−から8のアルキル基を有していてもよいフェノキシカルボニル基、炭素数１から８のアルキル基を有していてもよいアミノ基、炭素数１から８のアルキル基を有していてもよいカルバモイル基、ニトロ基、炭素数１から８のフルオロアルキル基、炭素数１から８のアルキル基を有していてもよいフェノキシ基、又はシクロへキシルオキシ基等が挙げられる。 Ar 2 includes an aromatic ring such as a phenyl group, a naphthyl group, a pyrrolyl group, a thiophenyl group, a furanyl group, an indolyl group, a benzofuranyl group, or a pyridyl group. These aromatic ring substituents include chlorine atoms, fluorine atoms, alkyl groups having 1 to 8 carbon atoms, phenyl groups optionally having 1 to 8 carbon atoms, alkenyl groups having 2 to 8 carbon atoms, Alkynyl group having 2 to 8 carbon atoms, alkoxy group having 1 to 8 carbon atoms, alkylthio group having 1 to 8 carbon atoms, cyano group, formyl group, acyl group having 2 to 8 carbon atoms, alkyl group having 1 to 8 carbon atoms A benzoyl group which may have a carbon atom, an alkoxycarbonyl group having 2 to 8 carbon atoms, a phenoxycarbonyl group which may have an alkyl group having 1 to 8 carbon atoms, and an alkyl group having 1 to 8 carbon atoms. And optionally having an amino group, a carbamoyl group optionally having an alkyl group having 1 to 8 carbon atoms, a nitro group, a fluoroalkyl group having 1 to 8 carbon atoms, and an alkyl group having 1 to 8 carbon atoms Feno that you may have Shi group or hexyloxy group and the like cyclohexylene.

Xとしてアルコキシ基を用いる場合、アルコキシ基として例えば炭素数1から８のアルキル基を有するアルコキシ基、炭素数1から８のアルキル基を有していてもよいフェノキシ基、シクロへキシルオキシ基、又は下式(VIII)のa,b,cまたはdで表される化合物(式VIII中、rは１から４の整数を表し、sおよびtはそれぞれ独立に0から５の整数を表し、Meはメチル基を表す)が挙げられる。
When an alkoxy group is used as X, for example, an alkoxy group having an alkyl group having 1 to 8 carbon atoms, a phenoxy group optionally having an alkyl group having 1 to 8 carbon atoms, a cyclohexyloxy group, or A compound of the formula (VIII) represented by a, b, c or d (wherein r represents an integer of 1 to 4, s and t each independently represents an integer of 0 to 5; Me represents methyl Represents a group).

Mとしてはカリウム、ナトリウム等が挙げられる。 Examples of M include potassium and sodium.

一般式(II)で示されるアリールボロン酸の具体例としては、フェニルボロン酸、o-トリルボロン酸、ｍ-トリルボロン酸、ｐ-トリルボロン酸、o-メトキシフェニルボロン酸、m-メトキシフェニルボロン酸、ｐ-メトキシフェニルボロン酸、4-アセトキシボロン酸、3,4-ジメトキシフェニルボロン酸、3,4-メチレンジオキシフェニルボロン酸、4-ブロモ-3-フルオロフェニルボロン酸、４‐（N,N−ジメチル）アミノフェニルボロン酸、1-ナフチルボロン酸、2-ナフチルボロン酸、2,3-ジヒドロベンゾフラニルボロン酸、２−ピローリルボロン酸、２−チオフェニルボロン酸、２−フラニルボロン酸が挙げられる。 又、式(II)のアリールボロン酸の誘導体としては、上記ボロン酸のトリフルオロカリウム塩が例示される。式(III)の具体例としては、上記したアリールボロン酸の無水物が挙げられる。 上記アリールボロン酸若しくはその誘導体、又はアリールボロン酸無水物の添加量は、α,β-不飽和-β-アリールカルボニル化合物(I)に対してモル比で０．１から５０程度とすることができ、好ましくはモル比で１から20程度の範囲である。 Specific examples of the arylboronic acid represented by the general formula (II) include phenylboronic acid, o-tolylboronic acid, m-tolylboronic acid, p-tolylboronic acid, o-methoxyphenylboronic acid, m-methoxyphenylboronic acid, p-methoxyphenylboronic acid, 4-acetoxyboronic acid, 3,4-dimethoxyphenylboronic acid, 3,4-methylenedioxyphenylboronic acid, 4-bromo-3-fluorophenylboronic acid, 4- (N, N -Dimethyl) aminophenylboronic acid, 1-naphthylboronic acid, 2-naphthylboronic acid, 2,3-dihydrobenzofuranylboronic acid, 2-pyrrolylboronic acid, 2-thiophenylboronic acid, 2-furanylboronic acid Can be mentioned. Examples of the arylboronic acid derivative of the formula (II) include the trifluoropotassium salt of boronic acid. Specific examples of the formula (III) include the arylboronic acid anhydrides described above. The amount of the arylboronic acid or derivative thereof or arylboronic acid anhydride added may be about 0.1 to 50 in molar ratio to the α, β-unsaturated-β-arylcarbonyl compound (I). Preferably, the molar ratio is in the range of about 1 to 20.

<パラジウム錯体触媒> パラジウム錯体触媒は、一般式（IV）PdYoL1 p(Chiraphos)q(式IV中、YはClO4、BF4、PF6、SbF6、OTf、ハロゲン原子、ヒドロキシ基、アルコキシ基、又はアシルオキシ基を表し、L１は有機配位子を表し、o,p,qはそれぞれ０から６の整数を表す。)で表される。 <Palladium complex catalyst> The palladium complex catalyst has the general formula (IV) PdY o L 1 p (Chiraphos) q (wherein Y is ClO 4 , BF 4 , PF 6 , SbF 6 , OTf, halogen atom, hydroxy group , An alkoxy group, or an acyloxy group, L 1 represents an organic ligand, and o, p, and q each represents an integer of 0 to 6.

Yの具体的な例としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子、ClO4,BF4,PF6又はSbF6アニオンなどが挙げられる。又、Yとして有機含酸素化合物を用いる場合の例としては、ヒドロキシ基、炭素数1から8のアルキル基を有するアルコキシ基、アセチルアセトナート基、トリフルオロメタンスルホナート基、又はアセトキシ基などが挙げられる。 Yとして好ましくはClO4,BF4,PF6,又はSbF6アニオンであり、特に好ましくはSbF6アニオンである。又、式IVのoは好ましくは２である。 Specific examples of Y include fluorine atom, chlorine atom, bromine atom, iodine atom, ClO 4 , BF 4 , PF 6 or SbF 6 anion. Examples of using an organic oxygen-containing compound as Y include a hydroxy group, an alkoxy group having an alkyl group having 1 to 8 carbon atoms, an acetylacetonate group, a trifluoromethanesulfonate group, or an acetoxy group. . Y is preferably ClO 4 , BF 4 , PF 6 , or SbF 6 anion, and particularly preferably SbF 6 anion. Also, o in Formula IV is preferably 2.

有機配位子L1としては、CO,NO,NH2,NH3の他、オレフィン類、アセチレン類、芳香族化合物類、有機含酸素化合物類、有機含窒素化合物類、又は有機含硫黄化合物類などが挙げられる。 オレフィン類化合物としては、例えばエチレン、アリル、ブタジエン、シクロヘキセン、1,3−シクロヘキサジエン、シクロオクテン(coe)、1,5−シクロオクタジエン(cod)、ノルボルナジエン(nbd)、アクリル酸エチル、メタクリル酸エステル、シクロペンタジエニル、又はペンタメチルシクロペンタジエニルなどが例示される。 アセチレン類化合物としてはアセチレン、1,2−ジメチルアセチレン、1,4−ペンタジイン、1,2−ジフェニルアセチレンなどが例示される。芳香族化合物としてはベンゼン、p−シメン、メシチレン、ヘキサメチルベンゼン、ナフタレン、アントラセンが例示される。有機含酸素化合物としては、アセテート、ベンゾエート、アセチルアセトナート、トリフルオロメタンスルホネートなどが例示される。有機含窒素化合物としてはアセトニトリル、ベンゾニトリル、プロピオニトリル、ブチロニトリル、t-ブチルイソシアニド、ピリジン、1,10−フェナントロリン2,2'-ビピリジルが例示される。有機含硫黄化合物としてはジメチルスルホキシド、ジメチルスルフィド、チオフェン、二硫化炭素、硫化炭素、チオフェノールなどが例示される。 As the organic ligand L 1, CO, NO, other NH 2, NH 3, olefins, acetylenes, aromatics, organic oxygen-containing compounds, organic nitrogen-containing compounds, or organic sulfur-containing compounds Etc. Examples of olefin compounds include ethylene, allyl, butadiene, cyclohexene, 1,3-cyclohexadiene, cyclooctene (coe), 1,5-cyclooctadiene (cod), norbornadiene (nbd), ethyl acrylate, and methacrylic acid. Examples include ester, cyclopentadienyl, pentamethylcyclopentadienyl, and the like. Examples of acetylene compounds include acetylene, 1,2-dimethylacetylene, 1,4-pentadiyne, and 1,2-diphenylacetylene. Examples of aromatic compounds include benzene, p-cymene, mesitylene, hexamethylbenzene, naphthalene, and anthracene. Examples of the organic oxygen-containing compound include acetate, benzoate, acetylacetonate, trifluoromethanesulfonate, and the like. Examples of the organic nitrogen-containing compound include acetonitrile, benzonitrile, propionitrile, butyronitrile, t-butylisocyanide, pyridine, and 1,10-phenanthroline 2,2′-bipyridyl. Examples of the organic sulfur-containing compound include dimethyl sulfoxide, dimethyl sulfide, thiophene, carbon disulfide, carbon sulfide, and thiophenol.

L1は好ましくはアセトニトリル、ベンゾニトリル、プロピオニトリル、ブチロニトリル等ニトリル化合物であり、さらに好ましくはベンゾニトリルである。又、式IVのpは好ましくは２である。 L 1 is preferably a nitrile compound such as acetonitrile, benzonitrile, propionitrile, butyronitrile, and more preferably benzonitrile. Also, p in formula IV is preferably 2.

Chiraphos（キラホス）（(2S,3S)-(-)-ビス(ジフェニルホスフィノ)ブタン、および（2R,3R)-(+)-ビス(ジフェニルホスフィノ)ブタン）は光学活性ホスフィン配位子であり、遷移金属を用いる不斉合成などに用いられ、二つのリン原子を持つホスフィンであり、配位子となる。キラホスには、(S,S)-および(R,R)-キラホスがある。 式IVのqは好ましくは１である。 Chiraphos ((2S, 3S)-(-)-bis (diphenylphosphino) butane and (2R, 3R)-(+)-bis (diphenylphosphino) butane) is an optically active phosphine ligand. Yes, it is a phosphine having two phosphorus atoms and used as an asymmetric synthesis using a transition metal. Chilafos includes (S, S)-and (R, R) -chilafos. Q in formula IV is preferably 1.

パラジウム錯体触媒（IV）は、例えばPdCl2(cod)(cod=1,5-シクロオクタジエン)のようなパラジウム前駆体と、chiraphosから調整されるPdCl2(Chiraphos)にAgSbF6のような銀塩とを用いて、ベンゾニトリル中でこれらを混合して得られる。ベンゾニトリルを他の有機配位子に変えることにより（IV）式中のLを変えることができ、上記パラジウム錯体中のSbF6を他の塩に変えることにより(IV)式中のYを変えることができる。パラジウム前駆体は、ジクロロ（1,5-シクロオクタジエン）パラジウム以外に、金属パラジウム、塩化パラジウム、酢酸パラジウム、ビス（アセチルアセトナト）パラジウム、トリス（ジベンジリデンアセトン）ニパラジウム、クロロアリルパラジウムダイマー、テトラクロロパラジウム酸カリウムなどのアルカリ金属塩などが使用できる。 本発明においては、このようにして得たパラジウム錯体触媒を反応系に導入してもよく、反応系に上記各成分を加え、反応系内でパラジウム錯体触媒を生成させてもよい。 上記のパラジウム錯体触媒におけるchiraphosの配合量は反応条件により異なるが、反応系内に共存するパラジウム元素（パラジウム錯体触媒中のＰｄ）に対するモル比で、0.1から50程度とすることができ、好ましくはモル比で0.9から5程度の範囲である。 又、上記(IV)で示されるパラジウム錯体触媒の添加量は反応基質（Ｉ式の化合物）に対するモル比で0.00001から0.5程度とすることができ、好ましくはモル比で0.0001から0.05程度の範囲である。 The palladium complex catalyst (IV) is composed of, for example, a palladium precursor such as PdCl 2 (cod) (cod = 1,5-cyclooctadiene), PdCl 2 prepared from chiraphos (Chiraphos) and silver such as AgSbF 6. Obtained by mixing them in benzonitrile with a salt. L in formula (IV) can be changed by changing benzonitrile to other organic ligands, and Y in formula (IV) can be changed by changing SbF 6 in the palladium complex to other salts. be able to. In addition to dichloro (1,5-cyclooctadiene) palladium, palladium precursors include metal palladium, palladium chloride, palladium acetate, bis (acetylacetonato) palladium, tris (dibenzylideneacetone) dipalladium, chloroallyl palladium dimer, Alkali metal salts such as potassium tetrachloropalladate can be used. In the present invention, the palladium complex catalyst thus obtained may be introduced into the reaction system, or the above components may be added to the reaction system to produce a palladium complex catalyst in the reaction system. The compounding amount of chiraphos in the above palladium complex catalyst varies depending on the reaction conditions, but the molar ratio to the palladium element (Pd in the palladium complex catalyst) coexisting in the reaction system can be about 0.1 to 50, preferably The molar ratio is in the range of about 0.9 to 5. The addition amount of the palladium complex catalyst represented by the above (IV) can be about 0.00001 to 0.5 in terms of molar ratio to the reaction substrate (compound of formula I), preferably in the range of about 0.0001 to 0.05 in terms of molar ratio. is there.

パラジウム錯体触媒（IV）中のＰｄの価数としては、二価カチオン性パラジウムが好ましい。 The valence of Pd in the palladium complex catalyst (IV) is preferably divalent cationic palladium.

<反応条件> 本発明においては通常、溶媒が用いられる。溶媒としては、反応原料、触媒系を可溶化するものが好ましく用いられる。溶媒の具体例としては、例えばトルエン、キシレンなどの芳香族溶媒、ペンタン、ヘキサンなどの脂肪族溶媒、塩化メチレンなどのハロゲン含有炭化水素溶媒、エーテル、テトラヒドロフラン、1,4−ジオキサンなどのエーテル溶媒、メタノール、エタノール、2−プロパノール、ブタノール、ベンジルアルコールなどのアルコール系溶媒、アセトンなどのケトン系溶媒、アセトニトリル、N,N-ジメチルホルムアミド、N-メチルピロリドン、ピリジン、ジメチルスルホキシドなどへテロ原子を含む有機溶媒、及び水を用いることができる。これら溶媒は単独でも、任意の割合で２種以上を混合して用いることもできる。 本発明における反応温度は通常、−40℃から200℃程度の範囲とすることができるが、好ましくは-10℃から120℃とすることができる。特に好ましくは0℃付近が良い。また、反応中に酸素による触媒の失活を防ぐため、反応は窒素ガス、アルゴンガス等の不活性ガス雰囲気で行うことが好ましい。反応時の圧力は特に制限されないが、通常大気圧でおこなわれる。 反応時間は反応基質濃度、温度等の条件によって異なるが通常、数分から30時間程度で完結する。 本発明における反応形式はバッチ式でも連続式でもよい。 <Reaction conditions> In the present invention, a solvent is usually used. As the solvent, those which solubilize the reaction raw materials and the catalyst system are preferably used. Specific examples of the solvent include aromatic solvents such as toluene and xylene, aliphatic solvents such as pentane and hexane, halogen-containing hydrocarbon solvents such as methylene chloride, ether solvents such as ether, tetrahydrofuran and 1,4-dioxane, Organic solvents containing heteroatoms such as methanol, ethanol, 2-propanol, butanol, alcohol solvents such as benzyl alcohol, ketone solvents such as acetone, acetonitrile, N, N-dimethylformamide, N-methylpyrrolidone, pyridine, dimethyl sulfoxide A solvent and water can be used. These solvents can be used alone or in admixture of two or more at any ratio. The reaction temperature in the present invention can usually be in the range of about -40 ° C to 200 ° C, preferably -10 ° C to 120 ° C. Particularly preferred is around 0 ° C. In order to prevent the catalyst from being deactivated by oxygen during the reaction, the reaction is preferably performed in an inert gas atmosphere such as nitrogen gas or argon gas. The pressure during the reaction is not particularly limited, but is usually carried out at atmospheric pressure. The reaction time varies depending on the conditions such as the concentration of the reaction substrate and temperature, but is usually completed within a few minutes to 30 hours. The reaction mode in the present invention may be batch type or continuous type.

<銀塩> 本発明において、銀塩を反応系に配合することが好ましい。銀塩としては、例えばテトラフルオロホウ酸銀、ヘキサフルオロアンチモン酸銀、ヘキサフルオロ燐酸銀、炭酸銀及び過塩素酸銀の群から選ばれる１種又は２種以上が挙げられる。銀塩の配合量はアリールボロン酸若しくはその誘導体、又はアリールボロン酸無水物に対してモル比で0.0001から5とすることができ、より好ましくはモル比で0.001から3である。 なお、銀塩として塩化銀、硝酸銀は有効でない。 <Silver salt> In the present invention, a silver salt is preferably added to the reaction system. Examples of the silver salt include one or more selected from the group consisting of silver tetrafluoroborate, silver hexafluoroantimonate, silver hexafluorophosphate, silver carbonate, and silver perchlorate. The compounding amount of the silver salt can be 0.0001 to 5 in molar ratio with respect to the aryl boronic acid or derivative thereof or aryl boronic anhydride, and more preferably 0.001 to 3 in molar ratio. Silver chloride and silver nitrate are not effective as silver salts.

<生成物> 上記一般式(I)の反応基質に対し、光学活性βージアリール電子吸引性基置換化合物が生成物として得られる。光学活性βージアリール電子吸引性基置換化合物の具体例としては、(S)-4-(3-メトキシフェニル)-4-フェニル-2-ブタノン、S)-1-(3-メトキシフェニル)-1-フェニル-3-ヘプタノン、(S)-1-(3-メトキシフェニル)-4-メチル−1−フェニル−3−ペンタノン、(S)-1-シクロへキシル-3-(3―メトキシフェニル)-3-フェニル-1-プロパノン、(S)-3-(3-メトキシフェニル)-1,3-ジフェニル-1-プロパノン、(S)-3-(3-メトキシフェニル)-1-(4-メトキシフェニル)-3-フェニル-1-プロパノン、(S)-3-(3-メトキシフェニル)-1-(4-ニトロフェニル)-3-フェニル-1-プロパノン、(S)-3-(3-メトキシフェニル)-3-(4-メトキシフェニル)-1-フェニル-1-プロパノン、(R)-4-(2-ベンジロキシ-5-メチルフェニル)-4-(3-メトキシフェニル)-2-ブタノン、(R)-3-(2-ベンジロキシ-5-メチルフェニル)-3-(3-メトキシフェニル)-1-フェニル-1-プロパノン、(S)-1,3-ジフェニル-3-(4-メチルフェニル)-1-プロパノン、(S)-4-(3-メトキシフェニル)-4-(2-ナフチル)-2-ブタノン、(S)-4-(4-アセトキシフェニル)-4-フェニル-2-ブタノン、(S)-4-(4-メトキシフェニル)-4-フェニル-2-ブタノン、(S)-4-(3,4-ジメトキシフェニル)-4-フェニル-2-ブタノン、及び(S)-4-(3,4-メチレンジオキシフェニル)-4-フェニル-2-ブタノン、並びにこれらの鏡像異性体等が挙げられる。 <Product> An optically active β-diaryl electron-withdrawing group-substituted compound is obtained as a product for the reaction substrate of the above general formula (I). Specific examples of the optically active β-diaryl electron-withdrawing group-substituted compound include (S) -4- (3-methoxyphenyl) -4-phenyl-2-butanone, S) -1- (3-methoxyphenyl) -1 -Phenyl-3-heptanone, (S) -1- (3-methoxyphenyl) -4-methyl-1-phenyl-3-pentanone, (S) -1-cyclohexyl-3- (3-methoxyphenyl) -3-phenyl-1-propanone, (S) -3- (3-methoxyphenyl) -1,3-diphenyl-1-propanone, (S) -3- (3-methoxyphenyl) -1- (4- Methoxyphenyl) -3-phenyl-1-propanone, (S) -3- (3-methoxyphenyl) -1- (4-nitrophenyl) -3-phenyl-1-propanone, (S) -3- (3 -Methoxyphenyl) -3- (4-methoxyphenyl) -1-phenyl-1-propanone, (R) -4- (2-benzyloxy-5-methylphenyl) -4- (3-methoxyphenyl) -2- Butanone, (R) -3- (2-Benzyloxy-5-methylphenyl) -3- (3-methoxyphenyl) -1-phenyl-1-prop Non, (S) -1,3-diphenyl-3- (4-methylphenyl) -1-propanone, (S) -4- (3-methoxyphenyl) -4- (2-naphthyl) -2-butanone, (S) -4- (4-acetoxyphenyl) -4-phenyl-2-butanone, (S) -4- (4-methoxyphenyl) -4-phenyl-2-butanone, (S) -4- (3 , 4-dimethoxyphenyl) -4-phenyl-2-butanone and (S) -4- (3,4-methylenedioxyphenyl) -4-phenyl-2-butanone and their enantiomers It is done.

<光学活性クロメン誘導体の製造> 本発明を適用することにより、光学活性クロメン誘導体（4H-クロメン誘導体）の前駆体となる2-クロマノール誘導体を高効率、高選択性で製造することができる。 2-クロマノール誘導体の製造に用いる反応基質としては、式(I)の化合物において、式(VI)
（式VI中、R１,R２はそれぞれ同一又は異なっていても良い水素又はアルキル基を表し、R3は水素、アルキル基、又は置換若しくは無置換のアリール基を表し、R4は塩素原子、フッ素原子、ヒドロキシ基、炭素数１から８のアルキル基、炭素数１から８のアルキル基を有していてもよいフェニル基、炭素数２から８のアルケニル基、炭素数２から８のアルキニル基、炭素数１から８のアルコキシ基、炭素数１から８のアルキルチオ基、シアノ基、ホルミル基、炭素数２から８のアシル基、炭素数１から８のアルキル基を有していてもよいベンゾイル基、炭素数２から８のアルコキシカルボニル基、炭素数１から８のアルキル基を有していてもよいフェノキシカルボニル基、炭素数１から８のアルキル基を有していてもよいアミノ基、炭素数１から８のアルキル基を有していてもよいカルバモイル基、ニトロ基、炭素数１から８のフルオロアルキル基、又は炭素数１から８のアルキル基を有していてもよいフェノキシ基を表す。）で表されるα,β-不飽和-β-アリールカルボニル化合物を用いる。 <Production of optically active chromene derivative> By applying the present invention, a 2-chromanol derivative that is a precursor of an optically active chromene derivative (4H-chromene derivative) can be produced with high efficiency and high selectivity. As the reaction substrate used for the production of the 2-chromanol derivative, in the compound of the formula (I), the formula (VI)
(In Formula VI, R 1 and R 2 each represent hydrogen or an alkyl group which may be the same or different, R 3 represents hydrogen, an alkyl group, or a substituted or unsubstituted aryl group, and R 4 represents a chlorine atom. , Fluorine atom, hydroxy group, alkyl group having 1 to 8 carbon atoms, phenyl group optionally having 1 to 8 carbon atoms, alkenyl group having 2 to 8 carbon atoms, alkynyl having 2 to 8 carbon atoms Group, an alkoxy group having 1 to 8 carbon atoms, an alkylthio group having 1 to 8 carbon atoms, a cyano group, a formyl group, an acyl group having 2 to 8 carbon atoms, and an alkyl group having 1 to 8 carbon atoms. A benzoyl group, an alkoxycarbonyl group having 2 to 8 carbon atoms, a phenoxycarbonyl group optionally having an alkyl group having 1 to 8 carbon atoms, an amino group optionally having an alkyl group having 1 to 8 carbon atoms, 1 carbon A carbamoyl group optionally having 8 alkyl groups, a nitro group, a fluoroalkyl group having 1 to 8 carbon atoms, or a phenoxy group optionally having an alkyl group having 1 to 8 carbon atoms. An α, β-unsaturated-β-arylcarbonyl compound represented by the formula:

そして、式(VI)の反応基質に対し、上記した場合と同様なアリールボロン酸若しくはその誘導体、又はアリールボロン酸無水物、を式(IV)のパラジウム錯体触媒存在下で反応させることにより、β-ジアリールカルボニル化合物の１種である2−クロマノール誘導体を製造することができる。 上記2−クロマノール誘導体は、一般式（VII）
(式VII中、Ar１
、Ar2、R1,R2,R3及びR4はそれぞれ式II〜Vに用いた置換基と同一である)で表される。 Then, by reacting the reaction substrate of the formula (VI) with the same aryl boronic acid or derivative thereof as described above or an aryl boronic acid anhydride in the presence of a palladium complex catalyst of the formula (IV), β A 2-chromanol derivative, which is one of diarylcarbonyl compounds, can be produced. The 2-chromanol derivative has the general formula (VII)
(In formula VII, Ar 1
, Ar 2 , R 1 , R 2 , R 3 and R 4 are respectively the same as the substituents used in formulas II to V).

そして、式（VII）の前駆体に対し、既知の脱水反応を施すことで光学活性クロメン誘導体を最終生成物として得ることができる。光学活性クロメン誘導体は天然生物活性物質であり、有用である。 本発明によって得られる光学活性クロメン誘導体の具体例としては、(+)-6-メトキシ-2-メチル-4-フェニル-4H-クロメン、(+)-2,4-ジフェニル-4H-クロメン、(+)-4-(4-メトキシフェニル)-2,6-ジメチル-4H-クロメン、(+)-4-(3-メトキシフェニル)-2,6-ジメチル-4H-クロメン、(+)-2,6-ジメチル-4-(3,4-メチレンジオキシフェニル)-4H-クロメン、(+)-2,6-ジメチル-4-(4-メチルフェニル)-4H-クロメン、(+)-2,6-ジメチル-4-フェニル-4H-クロメン、(+)-2,6-ジメチル-4-(4-アセトキシフェニル)-4H-クロメンおよびこれらの鏡像異性体等が挙げられる。 An optically active chromene derivative can be obtained as a final product by subjecting the precursor of formula (VII) to a known dehydration reaction. Optically active chromene derivatives are natural biologically active substances and are useful. Specific examples of the optically active chromene derivative obtained by the present invention include (+)-6-methoxy-2-methyl-4-phenyl-4H-chromene, (+)-2,4-diphenyl-4H-chromene, +)-4- (4-methoxyphenyl) -2,6-dimethyl-4H-chromene, (+)-4- (3-methoxyphenyl) -2,6-dimethyl-4H-chromene, (+)-2 , 6-Dimethyl-4- (3,4-methylenedioxyphenyl) -4H-chromene, (+)-2,6-Dimethyl-4- (4-methylphenyl) -4H-chromene, (+)-2 , 6-dimethyl-4-phenyl-4H-chromene, (+)-2,6-dimethyl-4- (4-acetoxyphenyl) -4H-chromene and their enantiomers.

以下、実施例により本発明を詳細に説明するが、本発明はこれにより限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by this.

光学活性β−ジアリールカルボニル化合物として、以下の表１に記載した各生成物５ａ〜５ｌを製造した。生成物５（５ａ〜５ｌ）の反応式IXを以下に示す。
As optically active β-diarylcarbonyl compounds, the products 5a to 5l described in Table 1 below were produced. Scheme IX for product 5 (5a-5l) is shown below.

(S)-4-(3-メトキシフェニル)-4-フェニル-2-ブタノン(5a)の合成 窒素雰囲気、アセトン(1ml)と水 (0.1ml)中で、ビス（ベンゾニトリル）（(2S,3S)-(-)-ビス(ジフェニルホスフィノ)ブタン）パラジウムヘキサフルオロアンチモン酸塩[Pd((S,S)-chiraphos)(PhCN)2]SbF6（0.01mmol,mol%）に対し、trans-4-フェニル-3-ブテン-2-オン(0.5mmol)、テトラフルオロホウ酸銀 (0.05mmol,10mol%)、3-メトキシフェニルボロン酸(0.6mmol)を加え0度で21時間攪拌した。反応液にエーテルを加え、飽和塩化アンモニウム水溶液で有機層を洗浄した。有機層に無水硫酸マグネシウムを加え乾燥後、ろ過し減圧濃縮し、残渣をシリカゲルクロマトグラフィー（ヘキサン：酢酸エチル＝３０：１〜１５：１）で精製し、表１の4-(3-メトキシフェニル)-4-フェニル-2-ブタノンを生成物として得た（122mg,96%）。 Synthesis of (S) -4- (3-methoxyphenyl) -4-phenyl-2-butanone (5a) In a nitrogen atmosphere, acetone (1 ml) and water (0.1 ml), bis (benzonitrile) ((2S, 3S)-(-)-bis (diphenylphosphino) butane) palladium hexafluoroantimonate [Pd ((S, S) -chiraphos) (PhCN) 2 ] SbF 6 (0.01 mmol, mol%) versus trans 4-Phenyl-3-buten-2-one (0.5 mmol), silver tetrafluoroborate (0.05 mmol, 10 mol%) and 3-methoxyphenylboronic acid (0.6 mmol) were added, and the mixture was stirred at 0 ° C. for 21 hours. Ether was added to the reaction solution, and the organic layer was washed with a saturated aqueous ammonium chloride solution. Anhydrous magnesium sulfate is added to the organic layer, dried, filtered and concentrated under reduced pressure. The residue is purified by silica gel chromatography (hexane: ethyl acetate = 30: 1 to 15: 1), and 4- (3-methoxyphenyl) in Table 1 is collected. ) -4-Phenyl-2-butanone was obtained as product (122 mg, 96%).

生成物の分析結果を以下に示す。キラルHPLC（DAICEL CHIRALCEL OD-H）を用い、溶媒としてヘキサン：イソプロピルアルコール＝９：１を用いて流速0.5ml/minで流し、生成物を測定したところ、二つの鏡像異性体の溶出時間は28分と32分であった。これより、生成物の鏡像異性体過剰率(%ee)を95%eeと同定した。 HPLC column,DAICEL CHIRALCEL OD-H: eluent, n-hexane/2-propanol (9:1): flow rate, 0.5 mL/min: tR 28 and 32 min; IR(neat);559, 697, 773, 1040, 1150, 1257, 1356, 1453, 1488, 1583, 1596, 1712 cm-1; 1HNMR(400 MHz, CDCl3) δ 2.08 (s, 3H), 3.16 (d, J = 7.6 Hz, 2H), 3.75 (s, 3H), 4.55 (t, J = 7.6 Hz, 1H), 6.70-6.77 (m, 2H), 6.81 (d, J = 7.8 Hz, 1H), 7.15-7.29 (m, 6H); 13CNMR(100 Hz, CDCl3) δ 30.44, 45.48, 49.36, 54.91, 111.17, 113.78, 119.86, 126.31, 127.49, 128.41, 129.39, 143.55, 145.33, 159.51, 206.65; MS(m/z) 43(27), 77 (13), 91(9.3), 103(97), 165 (37), 197 (56), 211 (81), 254(100, M+); exact mass calcd for C17H18O2: 254.1307; found 254.1303. [α]21 D(c in CHCl3): +2.8(0.43), 95%ee (OD-H, Hexane:iPrOH=9/1, tr=28, 32) The analysis results of the product are shown below. Using chiral HPLC (DAICEL CHIRALCEL OD-H), hexane: isopropyl alcohol = 9: 1 as a solvent, flowing at a flow rate of 0.5 ml / min, and measuring the product, the elution time of the two enantiomers was 28 Minutes and 32 minutes. From this, the enantiomeric excess (% ee) of the product was identified as 95% ee. HPLC column, DAICEL CHIRALCEL OD-H: eluent, n-hexane / 2-propanol (9: 1): flow rate, 0.5 mL / min: t R 28 and 32 min; IR (neat); 559, 697, 773, 1040, 1150, 1257, 1356, 1453, 1488, 1583, 1596, 1712 cm -1 ; 1 HNMR (400 MHz, CDCl3) δ 2.08 (s, 3H), 3.16 (d, J = 7.6 Hz, 2H), 3.75 (s, 3H), 4.55 (t, J = 7.6 Hz, 1H), 6.70-6.77 (m, 2H), 6.81 (d, J = 7.8 Hz, 1H), 7.15-7.29 (m, 6H); 13 CNMR (100 Hz, CDCl 3 ) δ 30.44, 45.48, 49.36, 54.91, 111.17, 113.78, 119.86, 126.31, 127.49, 128.41, 129.39, 143.55, 145.33, 159.51, 206.65; MS (m / z) 43 (27), 77 (13), 91 (9.3), 103 (97), 165 (37), 197 (56), 211 (81), 254 (100, M + ); exact mass calcd for C 17 H 18 O 2 : 254.1307; . found 254.1303 [α] 21 D (c in CHCl 3): +2.8 (0.43), 95% ee (OD-H, Hexane: iPrOH = 9/1, t r = 28, 32)

以下、式IXと同様にして、表１に示す基質とアリールボロン酸を用いて生成物５ｂ〜５ｌを得た。
Thereafter, in the same manner as in Formula IX, products 5b to 5l were obtained using the substrates shown in Table 1 and arylboronic acid.

各生成物５ｂ〜５ｌについての分析結果を以下に示す。 生成物：(S)-1-(3-メトキシフェニル)-1-フェニル-3-ヘプタノン(5b) HPLC column, DAICEL CHIRALCEL OJ-H: eluent, n-hexane/2-propanol (2:1): flow rate, 0.5 mL/min: tR 40 and 48 min; IR(neat);698, 775, 871, 1047, 1126, 1150, 1257, 1435, 1452, 1488, 1584, 1597, 1711, 2956 cm-1; 1HNMR(400 MHz, CDCl3) δ 0.82 (t, J = 7.1 Hz, 3H), 1.18 (hex, J = 7.6 Hz, 2H), 1.45 (quintet, J = 7.4 Hz, 2H), 2.31 (t, J = 7.4 Hz 2H), 3.13 (d, J = 7.4 Hz, 2H), 3.75 (s, 3H), 4.57 (t, J = 7.5 Hz, 1H), 6.69-6.76 (m, 3H), 7.14-7.28 (m, 6H); 13CNMR(100 Hz, CDCl3) δ 13.73, 22.08, 25.50, 43.22, 45.87, 48.58, 54.99, 111.2, 113.8, 120.0, 126.3, 127.6, 128.4, 129.4, 143.7, 145.5, 159.6, 209.0; MS(m/z) 103 (100), 133 (30), 165 (24), 197 (56), 211 (95), 239 (16), 296 (52, M+); exact mass calcd for C20H24O2: 296.1776; found 296.1773. [α]21 D(c in CHCl3): +3.0(0.89), 99%ee (OJ-H, Hexane:iPrOH=2/1, tr=40, 48) The analysis result about each product 5b-5l is shown below. Product: (S) -1- (3-methoxyphenyl) -1-phenyl-3-heptanone (5b) HPLC column, DAICEL CHIRALCEL OJ-H: eluent, n-hexane / 2-propanol (2: 1): flow rate, 0.5 mL / min: t R 40 and 48 min; IR (neat); 698, 775, 871, 1047, 1126, 1150, 1257, 1435, 1452, 1488, 1584, 1597, 1711, 2956 cm -1 ; 1 HNMR (400 MHz, CDCl3) δ 0.82 (t, J = 7.1 Hz, 3H), 1.18 (hex, J = 7.6 Hz, 2H), 1.45 (quintet, J = 7.4 Hz, 2H), 2.31 (t, J = 7.4 Hz 2H), 3.13 (d, J = 7.4 Hz, 2H), 3.75 (s, 3H), 4.57 (t, J = 7.5 Hz, 1H), 6.69-6.76 (m, 3H), 7.14-7.28 (m, 6H); 13 C NMR (100 Hz, CDCl 3 ) δ 13.73, 22.08, 25.50, 43.22, 45.87, 48.58, 54.99, 111.2, 113.8, 120.0, 126.3, 127.6, 128.4, 129.4, 143.7, 145.5, 159.6, 209.0; MS (m / z) 103 (100), 133 (30), 165 (24), 197 (56), 211 (95), 239 (16), 296 (52, M + ); exact mass calcd for C 20 H 24 O 2:. 296.1776; found 296.1773 [α] 21 D (c in CHCl 3): +3.0 (0.89), 99% ee (OJ-H, Hexane: iPrOH = 2/1, t r = 40 , 48)

生成物：(S)-1-(3-メトキシフェニル)-4-メチル−1−フェニル−3−ペンタノン (5c) HPLC column, DAICEL CHIRALPAK AD-H: eluent, n-hexane/2-propanol (99:1): flow rate, 0.5 mL/min: tR 32 and 34 min; IR(neat. cm-1): 2967, 1709, 1596, 1584, 1488, 1452, 1257, 1045, 698; 1HNMR(400 Hz, CDCl3): δ 7.28-7.14 (m, 6H), 6.81 (d, J = 7.7 Hz, 1H), 6.77-6.69 (m, 2H), 4.59 (t, J = 7.4 Hz, 1H), 3.75 (s, 3H), 3.18 (d, J = 7.4 Hz, 2H), 2.49 (sept, J = 7.0 Hz, 1H), 0.99 (d, J = 7.0 Hz, 3H), 0.98 (d, J = 7.0 Hz, 3H); 13CNMR(400 Hz, CDCl3): δ 212.3, 159.6, 145.7, 143.9, 129.4, 128.4, 127.6, 126.3, 120.0, 113.9, 111.2, 55.0, 46.4, 45.7, 41.3, 17.8 ; MS(m/z): 103 (54), 165 (28), 197(100), 211(72), 239(38), 282(70, M+); exact mass calcd for C19H22O2: 282.1620; found 282.1620; [α]23 D(c in CHCl3): +5.0 δ(0.56), 95%ee (AD-H, Hexane:iPrOH=99/1, tr=32, 34) Product: (S) -1- (3-methoxyphenyl) -4-methyl-1-phenyl-3-pentanone (5c) HPLC column, DAICEL CHIRALPAK AD-H: eluent, n-hexane / 2-propanol (99 : 1): flow rate, 0.5 mL / min: t R 32 and 34 min; IR (neat.cm -1 ): 2967, 1709, 1596, 1584, 1488, 1452, 1257, 1045, 698; 1 HNMR (400 Hz, CDCl 3 ): δ 7.28-7.14 (m, 6H), 6.81 (d, J = 7.7 Hz, 1H), 6.77-6.69 (m, 2H), 4.59 (t, J = 7.4 Hz, 1H), 3.75 (s, 3H), 3.18 (d, J = 7.4 Hz, 2H), 2.49 (sept, J = 7.0 Hz, 1H), 0.99 (d, J = 7.0 Hz, 3H), 0.98 (d, J = 7.0 Hz , 3H); 13 C NMR (400 Hz, CDCl 3 ): δ 212.3, 159.6, 145.7, 143.9, 129.4, 128.4, 127.6, 126.3, 120.0, 113.9, 111.2, 55.0, 46.4, 45.7, 41.3, 17.8; MS (m / z): 103 (54), 165 (28), 197 (100), 211 (72), 239 (38), 282 (70, M + ); exact mass calcd for C 19 H 22 O 2 : 282.1620; found 282.1620; [α] 23 D (c in CHCl 3): +5.0 δ (0.56), 95% ee (AD-H, Hexane: iPrOH = 99/1, t r = 32, 34)

生成物：(S)-1-シクロへキシル-3-(3―メトキシフェニル)-3-フェニル-1-プロパノン (5d) HPLC column, DAICEL CHIRALPAK AD-H: eluent, n-hexane/2-propanol (99.5:0.5): flow rate, 0.5 mL/min: tR 67 and 73 min; IR(neat. cm-1): 2927, 2852, 1705, 1596, 1583, 1488, 1449, 1257, 1046, 699; 1HNMR(400 Hz, CDCl3): δ 7.27-7.14(m, 6H), 6.82-6.69 (m, 3H), 4.59 (t, J = 7.8 Hz, 1H), 3.75 (dd, J = 1.9, 8.3 Hz, 1H), 3.17 (d, J = 7.8 Hz, 2H), 2.24 (m, 1H), 1.72-1.60 (m, 5H), 1.24-1.12 (m, 5H); 13CNMR(400 Hz, CDCl3): δ 211.5, 159.6, 145.8, 144.0, 129.4, 128.4, 127.7, 126.2, 120.0, 113.9, 111.2, 55.0, 51.2, 46.7, 45.5, 28.1, 25.7, 25.5; MS(m/z): 55 (34), 83 (38), 103 (69), 165 (29), 197 (100), 211 (96), 239 (50), 322 (55, M+); exact mass calcd for C22H26O2: 322.1933; found 322.1936; [α]23 D(c in CHCl3): +5.7 δ(0.80), 95%ee (AD-H, Hexane:iPrOH=99.5/0.5, tr=67, 73) Product: (S) -1-Cyclohexyl-3- (3-methoxyphenyl) -3-phenyl-1-propanone (5d) HPLC column, DAICEL CHIRALPAK AD-H: eluent, n-hexane / 2-propanol (99.5: 0.5): flow rate, 0.5 mL / min: t R 67 and 73 min; IR (neat.cm -1 ): 2927, 2852, 1705, 1596, 1583, 1488, 1449, 1257, 1046, 699; 1 HNMR (400 Hz, CDCl 3 ): δ 7.27-7.14 (m, 6H), 6.82-6.69 (m, 3H), 4.59 (t, J = 7.8 Hz, 1H), 3.75 (dd, J = 1.9, 8.3 Hz, 1H), 3.17 (d, J = 7.8 Hz, 2H), 2.24 (m, 1H), 1.72-1.60 (m, 5H), 1.24-1.12 (m, 5H); 13 CNMR (400 Hz, CDCl 3 ): δ 211.5, 159.6, 145.8, 144.0, 129.4, 128.4, 127.7, 126.2, 120.0, 113.9, 111.2, 55.0, 51.2, 46.7, 45.5, 28.1, 25.7, 25.5; MS (m / z): 55 (34) , 83 (38), 103 (69), 165 (29), 197 (100), 211 (96), 239 (50), 322 (55, M + ); exact mass calcd for C 22 H 26 O 2 : 322.1933; found 322.1936; [α] 23 D (c in CHCl 3): +5.7 δ (0.80), 95% ee (AD-H, Hexane: iPrOH = 99.5 / 0.5, t r = 67, 73)

生成物：(S)-3-(3-メトキシフェニル)-1,3-ジフェニル-1-プロパノン(5e) HPLC column, DAICEL CHIRALCEL OD-H: eluent, n-hexane/2-propanol (9:1): flow rate, 0.5 mL/min: tR 28 and 32 min; IR(neat);553, 691, 725, 750, 872, 922, 983, 1042, 1077, 1149, 1203, 1256, 1361, 1448, 1487, 1582, 1596, 1682 cm-1; 1HNMR(400 MHz, CDCl3) δ 3.73 (s, 3H), 4.79 (t, J = 7.3 Hz, 1H), 6.96-6.72 (ddd, J = 0.8, 2.6, 8.2 Hz 1H), 6.81 (t, J = 2.1 Hz, 1H), 6.86 (d, J = 7.8 Hz, 1H), 7.16-7.26 (m, 6H), 7.42 (t, J = 7.6 Hz, 2H), 7.55 (tt, J = 1.3, 7.4, 7.5 Hz, 1H), 7.92 (d, J = 7.1 Hz, 2H); 13CNMR(100 Hz, CDCl3) δ 44.48, 45.80, 54.93, 111.2, 113.0, 120.1, 126.3, 127.7, 127.9, 128.4, 129.4, 132.9, 136.9, 143.9, 145.7, 159.5, 197.8; MS(m/z) 77 (45), 103 (86), 105 (100), 133 (23), 165 (22), 197 (42), 211 (69), 316 (63, M+)exact mass calcd for C22H20O2: 316.1463; found 316.1465. [α]21 D(c in CHCl3): +7.1(0.71), 97%ee (OD-H, Hexane:iPrOH=95/5, tr=28, 32) Product: (S) -3- (3-methoxyphenyl) -1,3-diphenyl-1-propanone (5e) HPLC column, DAICEL CHIRALCEL OD-H: eluent, n-hexane / 2-propanol (9: 1 ): flow rate, 0.5 mL / min: t R 28 and 32 min; IR (neat); 553, 691, 725, 750, 872, 922, 983, 1042, 1077, 1149, 1203, 1256, 1361, 1448, 1487, 1582, 1596, 1682 cm -1 ; 1 HNMR (400 MHz, CDCl3) δ 3.73 (s, 3H), 4.79 (t, J = 7.3 Hz, 1H), 6.96-6.72 (ddd, J = 0.8, 2.6 , 8.2 Hz 1H), 6.81 (t, J = 2.1 Hz, 1H), 6.86 (d, J = 7.8 Hz, 1H), 7.16-7.26 (m, 6H), 7.42 (t, J = 7.6 Hz, 2H) , 7.55 (tt, J = 1.3, 7.4, 7.5 Hz, 1H), 7.92 (d, J = 7.1 Hz, 2H); 13 CNMR (100 Hz, CDCl 3 ) δ 44.48, 45.80, 54.93, 111.2, 113.0, 120.1 , 126.3, 127.7, 127.9, 128.4, 129.4, 132.9, 136.9, 143.9, 145.7, 159.5, 197.8; MS (m / z) 77 (45), 103 (86), 105 (100), 133 (23), 165 (22), 197 (42), 211 (69), 316 (63, M + ) exact mass calcd for C 22 H 20 O 2 : 316.1463; found 316.1465. [Α] 21 D (c in CHCl 3 ): + 7.1 (0.71), 97% ee (OD-H, Hexane: iPrOH = 95/5, t r = 28, 32)

生成物：(S)-3-(3-メトキシフェニル)-1-(4-メトキシフェニル)-3-フェニル-1-プロパノン(5f) HPLC column, DAICEL CHIRALCEL OD-H: eluent, n-hexane/2-propanol (4:1): flow rate, 0.5 mL/min: tR 22 and 25 min; IR(neat. cm-1): 1673, 1597, 1252, 1167, 697; 1HNMR(400 Hz, CDCl3): δ 7.93(d, J = 8.8 Hz, 2H), 7.26-7.14 (m, 6H), 6.92-6.80(m, 5H), 6.70 (dd, J = 1.9, 8.3 Hz, 1H), 4.79 (t, J = 7.3 Hz, 1H), 3.85 (s, 3H), 3.74 (s, 3H), 3.66 (d, J = 7.3 Hz, 2H); 13CNMR(100 Hz, CDCl3): δ 196.4, 163.4, 159.6, 145.8, 144.1, 130.3, 130.2, 130.1, 129.4, 128.5, 128.4, 127.79, 127.75, 126.3, 120.2, 114.0, 113.69, 113.66, 111.2, 55.4, 55.3, 55.1, 55.0, 46.0, 44.2; MS(m/z): 77 (12), 103 (24), 135 (100), 197(22), 211 (36), 346 (51, M+); exact mass calcd for C23H22O3: 346.1569; found 346.1565; [α]23 D(c in CHCl3): +10.6 δ(0.63), 95%ee (OD-H, Hexane:iPrOH=4/1, tr=22, 25) Product: (S) -3- (3-methoxyphenyl) -1- (4-methoxyphenyl) -3-phenyl-1-propanone (5f) HPLC column, DAICEL CHIRALCEL OD-H: eluent, n-hexane / 2-propanol (4: 1): flow rate, 0.5 mL / min: t R 22 and 25 min; IR (neat.cm -1 ): 1673, 1597, 1252, 1167, 697; 1 HNMR (400 Hz, CDCl 3 ): δ 7.93 (d, J = 8.8 Hz, 2H), 7.26-7.14 (m, 6H), 6.92-6.80 (m, 5H), 6.70 (dd, J = 1.9, 8.3 Hz, 1H), 4.79 ( t, J = 7.3 Hz, 1H), 3.85 (s, 3H), 3.74 (s, 3H), 3.66 (d, J = 7.3 Hz, 2H); 13 C NMR (100 Hz, CDCl 3 ): δ 196.4, 163.4 , 159.6, 145.8, 144.1, 130.3, 130.2, 130.1, 129.4, 128.5, 128.4, 127.79, 127.75, 126.3, 120.2, 114.0, 113.69, 113.66, 111.2, 55.4, 55.3, 55.1, 55.0, 46.0, 44.2; MS (m / z): 77 (12), 103 (24), 135 (100), 197 (22), 211 (36), 346 (51, M + ); exact mass calcd for C 23 H 22 O 3 : 346.1569; found 346.1565; [α] 23 D (c in CHCl 3): +10.6 δ (0.63), 95% ee (OD-H, Hexane: iPrOH = 4/1, t r = 22, 25)

生成物：(S)-3-(3-メトキシフェニル)-1-(4-ニトロフェニル)-3-フェニル-1-プロパノン(5g) HPLC column, DAICEL CHIRALCEL OD-H: eluent, n-hexane/2-propanol (2:1): flow rate, 0.5 mL/min: tR 114 and 131 min; IR(neat, cm-1): 1691, 1515, 1345, 1257, 1045, 852, 771, 733, 699; 1HNMR(400 Hz, CDCl3) δ 8.27 (d, J = 8.8 Hz, 2H), 8.04(d, J = 8.8 Hz, 2H), 7.27-7.18(m, 7H), 6.85(d, J = 7.3 Hz, 1H), 6.79 (s, 1H), 6.74-6.72(m, 1H), 4.76(t, J = 7.3 Hz, 1H), 3.76-3.74 (m, 5H); 13CNMR(400 Hz, CDCl3) δ 196.5, 159.6, 150.1, 145.0, 143.3, 141.3, 129.5, 128.9, 128.5, 127.6, 126.5, 123.7, 119.9, 114.0, 111.2, 55.0, 45.8, 45.0; MS(m/z) 103(90), 133(26), 165(33), 197(66), 211(100), 361(64, M+); exact mass calcd for C22H19NO4: 361.1314; found 361.1313; [α]23 D(c in CHCl3): +9.1(0.42), 92%ee (OD-H, Hexane:iPrOH=2/1, tr=114, 131) Product: (S) -3- (3-methoxyphenyl) -1- (4-nitrophenyl) -3-phenyl-1-propanone (5 g) HPLC column, DAICEL CHIRALCEL OD-H: eluent, n-hexane / 2-propanol (2: 1): flow rate, 0.5 mL / min: t R 114 and 131 min; IR (neat, cm -1 ): 1691, 1515, 1345, 1257, 1045, 852, 771, 733, 699 ; 1 HNMR (400 Hz, CDCl 3 ) δ 8.27 (d, J = 8.8 Hz, 2H), 8.04 (d, J = 8.8 Hz, 2H), 7.27-7.18 (m, 7H), 6.85 (d, J = 7.3 Hz, 1H), 6.79 (s, 1H), 6.74-6.72 (m, 1H), 4.76 (t, J = 7.3 Hz, 1H), 3.76-3.74 (m, 5H); 13 CNMR (400 Hz, CDCl 3 ) δ 196.5, 159.6, 150.1, 145.0, 143.3, 141.3, 129.5, 128.9, 128.5, 127.6, 126.5, 123.7, 119.9, 114.0, 111.2, 55.0, 45.8, 45.0; MS (m / z) 103 (90), 133 (26), 165 (33), 197 (66), 211 (100), 361 (64, M + ); exact mass calcd for C 22 H 19 NO 4 : 361.1314; found 361.1313; [α] 23 D ( c in CHCl 3): +9.1 ( 0.42), 92% ee (OD-H, Hexane: iPrOH = 2/1, t r = 114, 131)

生成物：(S)-3-(3-メトキシフェニル)-3-(4-メトキシフェニル)-1-フェニル-1-プロパノン(5h) HPLC column, DAICEL CHIRALCEL OD-H: eluent, n-hexane/2-propanol (9:1): flo
w rate, 0.5 mL/min: tR 21 and 27 min; IR(neat, cm-1): 1683, 1597, 1582, 1509, 1448, 1245, 1178, 1034, 691; 1HNMR(400 Hz, CDCl3) δ 7.92(d, J = 7.3 Hz, 2H), 7.54(t, J = 7.3 Hz, 1H), 7.43(t, J = 7.8 Hz, 2H), 7.2-7.1(m, 3H), 6.84(d, J = 7.8 Hz, 1H), 6.91-6.69(m, 4H), 4.74(t, J = 7.3 Hz, 1H), 3.74(s, 6H), 3.68(d, J = 7.3 Hz, 2H); 13CNMR(400 Hz, CDCl3) δ 197.8, 159.5, 157.9, 146.0, 136.9, 135.9, 132.8, 129.3, 128.5, 128.4, 127.8, 119.9, 113.8, 113.7, 111.0, 55.0, 54.9, 45.0, 44.6; MS(m/z) 77(15), 105(13), 133(20), 227(100), 346(24, M+); exact mass calcd for C23H22O3: 346.1569; found 346.1565; [α]23 D(c in CHCl3): +2.8(1.01), 99%ee (OD-H, Hexane:iPrOH=9/1, tr=21, 27) Product: (S) -3- (3-methoxyphenyl) -3- (4-methoxyphenyl) -1-phenyl-1-propanone (5h) HPLC column, DAICEL CHIRALCEL OD-H: eluent, n-hexane / 2-propanol (9: 1): flo
w rate, 0.5 mL / min: t R 21 and 27 min; IR (neat, cm -1 ): 1683, 1597, 1582, 1509, 1448, 1245, 1178, 1034, 691; 1 HNMR (400 Hz, CDCl 3 ) δ 7.92 (d, J = 7.3 Hz, 2H), 7.54 (t, J = 7.3 Hz, 1H), 7.43 (t, J = 7.8 Hz, 2H), 7.2-7.1 (m, 3H), 6.84 (d , J = 7.8 Hz, 1H), 6.91-6.69 (m, 4H), 4.74 (t, J = 7.3 Hz, 1H), 3.74 (s, 6H), 3.68 (d, J = 7.3 Hz, 2H); 13 CNMR (400 Hz, CDCl 3 ) δ 197.8, 159.5, 157.9, 146.0, 136.9, 135.9, 132.8, 129.3, 128.5, 128.4, 127.8, 119.9, 113.8, 113.7, 111.0, 55.0, 54.9, 45.0, 44.6; MS (m / z) 77 (15), 105 (13), 133 (20), 227 (100), 346 (24, M + ); exact mass calcd for C 23 H 22 O 3 : 346.1569; found 346.1565; [α] 23 D (c in CHCl 3) : +2.8 (1.01), 99% ee (OD-H, Hexane: iPrOH = 9/1, t r = 21, 27)

生成物：(R)-4-(2-ベンジロキシ-5-メチルフェニル)-4-(3-メトキシフェニル)-2-ブタノン(5i) HPLC column, DAICEL CHIRALPAK AD-H: eluent, n-hexane/2-propanol (9:1): flow rate, 0.5 mL/min: tR 13 and 16 min; IR(neat, cm-1): 1712, 1496, 1235, 1021, 804, 734, 695; 1HNMR(400 Hz, CDCl3) δ 7.35-7.14(m, 10H), 6.93-6.94(m, 2H), 6.77(d, , J = 8.7 Hz, 1H), 5.03-4.95(m, 3H), 3.13(d, J = 7.8 Hz, 2H), 2.24(s, 3H), 2.03(s, 3H); 13CNMR(400 Hz, CDCl3) δ 207.3, 153.6, 143.4, 137.1, 132.0, 129.8, 128.6, 128.3, 128.2, 127.9, 127.7, 127.6, 127.2, 126.0, 112.0, 70.1, 48.8, 39.8, 30.0, 20.6; MS(m/z) 91(100), 149(14), 211(22), 253(56), 344(4, M+); exact mass calcd for C29H26O2: 406.1933; found 406.1936; [α]21 D(c in CHCl3): +13.9(0.67), 96%ee (AD-H, Hexane:iPrOH=9/1, tr=13, 16) Product: (R) -4- (2-Benzyloxy-5-methylphenyl) -4- (3-methoxyphenyl) -2-butanone (5i) HPLC column, DAICEL CHIRALPAK AD-H: eluent, n-hexane / 2-propanol (9: 1): flow rate, 0.5 mL / min: t R 13 and 16 min; IR (neat, cm -1 ): 1712, 1496, 1235, 1021, 804, 734, 695; 1 HNMR ( 400 Hz, CDCl 3 ) δ 7.35-7.14 (m, 10H), 6.93-6.94 (m, 2H), 6.77 (d,, J = 8.7 Hz, 1H), 5.03-4.95 (m, 3H), 3.13 (d , J = 7.8 Hz, 2H), 2.24 (s, 3H), 2.03 (s, 3H); 13 CNMR (400 Hz, CDCl 3 ) δ 207.3, 153.6, 143.4, 137.1, 132.0, 129.8, 128.6, 128.3, 128.2 , 127.9, 127.7, 127.6, 127.2, 126.0, 112.0, 70.1, 48.8, 39.8, 30.0, 20.6; MS (m / z) 91 (100), 149 (14), 211 (22), 253 (56), 344 (4, M + ); exact mass calcd for C 29 H 26 O 2 : 406.1933; found 406.1936; [α] 21 D (c in CHCl 3 ): +13.9 (0.67), 96% ee (AD-H, Hexane : iPrOH = 9/1, t r = 13, 16)

生成物：(R)-3-(2-ベンジロキシ-5-メチルフェニル)-3-(3-メトキシフェニル)-1-フェニル-1-プロパノン(5j) HPLC column, DAICEL CHIRALPAK AD-H: eluent, n-hexane/2-propanol (15:1): flow rate, 0.5 mL/min: tR 20 and 30 min; IR(neat, cm-1): 1679, 1496, 1450, 1235, 735, 695, 681; 1HNMR(400 Hz, CDCl3) δ 7.89-7.87(m, 2H), 7.52-7.49(m, 1H), 7.39-7.14(m, 12H), 6.98-6.93(m, 2H), 6.77(d, , J = 8.5 Hz, 1H), 5.16 (t, J = 7.8 Hz, 1H), 4.99(d, J = 3.0 Hz, 2H), 3.70(d, 7.8 Hz, 2H), 2.23(s, 3H); 13CNMR(400 Hz, CDCl3) δ 198.4, 153.8, 143.6, 137.2, 137.1, 132.7, 132.4, 129.8, 129.0, 128.44, 128.40, 128.18, 128.16, 128.0, 127.7, 127.6, 127.3, 125.9, 112.1, 70.1, 43.7, 40.2, 20.7; MS(m/z) 91(70), 105(100), 211(17), 315(41), 406(5, M+); exact mass calcd for C29H26O2: 406.1933; found 406.1936; [α]21 D(c in CHCl3): +13.0(0.75), 98%ee (AD-H, Hexane:iPrOH=15/1, tr=22, 30) Product: (R) -3- (2-Benzyloxy-5-methylphenyl) -3- (3-methoxyphenyl) -1-phenyl-1-propanone (5j) HPLC column, DAICEL CHIRALPAK AD-H: eluent, n-hexane / 2-propanol (15: 1): flow rate, 0.5 mL / min: t R 20 and 30 min; IR (neat, cm -1 ): 1679, 1496, 1450, 1235, 735, 695, 681 ; 1 HNMR (400 Hz, CDCl 3 ) δ 7.89-7.87 (m, 2H), 7.52-7.49 (m, 1H), 7.39-7.14 (m, 12H), 6.98-6.93 (m, 2H), 6.77 (d ,, J = 8.5 Hz, 1H), 5.16 (t, J = 7.8 Hz, 1H), 4.99 (d, J = 3.0 Hz, 2H), 3.70 (d, 7.8 Hz, 2H), 2.23 (s, 3H) ; 13 CNMR (400 Hz, CDCl 3 ) δ 198.4, 153.8, 143.6, 137.2, 137.1, 132.7, 132.4, 129.8, 129.0, 128.44, 128.40, 128.18, 128.16, 128.0, 127.7, 127.6, 127.3, 125.9, 112.1, 70.1 , 43.7, 40.2, 20.7; MS (m / z) 91 (70), 105 (100), 211 (17), 315 (41), 406 (5, M + ); exact mass calcd for C 29 H 26 O 2: 406.1933; found 406.1936; [ α] 21 D (c in CHCl 3): +13.0 (0.75), 98% ee (AD-H, Hexane: iPrOH = 15/1, t r = 22, 30)

生成物：(S)-1,3-ジフェニル-3-(4-メチルフェニル)-1-プロパノン(5k) HPLC column, DAICEL CHIRALCEL OD-H: eluent, n-hexane/2-propanol (99.5:0.5): flow rate, 0.5 mL/min: tR 31 and 34 min; IR(neat); 822, 1678 cm-1; 1HNMR(400 Hz, CDCl3) δ 2.28 (s, 3H), 3.72 (d, J = 7.3 Hz, 2H), 4.79(t, J = 7.3 Hz, 1H), 7.06-7.08 (m, 2H), 7.17-7.79 (m, 3H), 7.23-7.26 (m, 4H), 7.41-7.45 (m, 2H), 7.52-7.55 (m, 1H), 7.92-7.94 (m, 2H); 13CNMR(400 Hz, CDCl3) δ 20.95, 44.77, 45.52, 126.26, 127.65, 127.75, 128.03, 128.51, 128.55, 129.23, 133.00, 135.85, 137.06, 141.11, 144.36, 198.04; MS(m/z) 77 (36), 91 (6), 105 (98), 117 (10), 165 (27), 181 (100), 195 (23), 300(35, M+); exact mass calcd for C22H20O: 300.1514; found 300.1517. [α]21 D(c in CHCl3): +7.9(0.54), 95%ee (OD-H, Hexane:iPrOH=99.5/0.5, tr=31, 34) Product: (S) -1,3-diphenyl-3- (4-methylphenyl) -1-propanone (5k) HPLC column, DAICEL CHIRALCEL OD-H: eluent, n-hexane / 2-propanol (99.5: 0.5 ): flow rate, 0.5 mL / min: t R 31 and 34 min; IR (neat); 822, 1678 cm -1 ; 1 HNMR (400 Hz, CDCl 3 ) δ 2.28 (s, 3H), 3.72 (d, J = 7.3 Hz, 2H), 4.79 (t, J = 7.3 Hz, 1H), 7.06-7.08 (m, 2H), 7.17-7.79 (m, 3H), 7.23-7.26 (m, 4H), 7.41-7.45 (m, 2H), 7.52-7.55 (m, 1H), 7.92-7.94 (m, 2H); 13 CNMR (400 Hz, CDCl 3 ) δ 20.95, 44.77, 45.52, 126.26, 127.65, 127.75, 128.03, 128.51, 128.55, 129.23, 133.00, 135.85, 137.06, 141.11, 144.36, 198.04; MS (m / z) 77 (36), 91 (6), 105 (98), 117 (10), 165 (27), 181 (100 ), 195 (23), 300 (35, M + ); exact mass calcd for C 22 H 20 O: 300.1514; found 300.1517. [Α] 21 D (c in CHCl 3 ): +7.9 (0.54), 95% ee (OD-H, Hexane: iPrOH = 99.5 / 0.5, t r = 31, 34)

生成物：(S)-4-(3-メトキシフェニル)-4-(2-ナフチル)-2-ブタノン(5l) HPLC column, DAICEL CHIRALCEL OD-H: eluent, n-hexane/2-propanol (9:1): flow rate, 0.5 mL/min: tR 39 and 41 min; IR(neat);543, 622, 659, 694, 717, 755, 785, 818, 858, 953, 1041, 1092, 1150, 1258, 1316, 1357, 1434, 1453, 1487, 1582, 1597, 1713 cm-1; 1HNMR(400 MHz, CDCl3) δ 2.11 (s, 3H), 3.27 (dd, J = 2.7, 7.5 Hz, 2H), 3.76 (s, 3H), 4.73 (t, J = 7.5 Hz 1H), 6.72 (dd, J = 2.5, 8.3 Hz, 1H), 6.80 (m, 1H), 6.86 (d, J = 7.8 Hz, 1H), 7.20 (t, J = 7.8 Hz, 1H), 7.32 (dd, J = 1.8, 8.6, 7.5 Hz, 1H), 7.40-7.46 (m, 2H), 7.67 (s, 1H), 7.76 (d, J = 8.6 Hz, 1H), 7.76-7.79 (m, 2H); 13CNMR(100 Hz, CDCl3) δ 30.54, 45.90, 49.23, 54.68, 111.2, 114.0, 120.1, 125.5, 126.0, 126.4, 127.4, 127.6, 128.2, 129.5, 132.1, 133.3, 141.0, 145.2, 160.0, 206.7; MS(m/z) 133 (51), 153 (51), 215 (33), 247 (100), 261 (30), 304 (82, M+)exact mass calcd for C21H20O2: 304.1463; found 604.1475. [α]21 D(c in CHCl3): -30(0.23), 96%ee (OD-H, Hexane:iPrOH=9/1, tr=39, 41) Product: (S) -4- (3-methoxyphenyl) -4- (2-naphthyl) -2-butanone (5l) HPLC column, DAICEL CHIRALCEL OD-H: eluent, n-hexane / 2-propanol (9 : 1): flow rate, 0.5 mL / min: t R 39 and 41 min; IR (neat); 543, 622, 659, 694, 717, 755, 785, 818, 858, 953, 1041, 1092, 1150, 1258, 1316, 1357, 1434, 1453, 1487, 1582, 1597, 1713 cm -1 ; 1 HNMR (400 MHz, CDCl3) δ 2.11 (s, 3H), 3.27 (dd, J = 2.7, 7.5 Hz, 2H) , 3.76 (s, 3H), 4.73 (t, J = 7.5 Hz 1H), 6.72 (dd, J = 2.5, 8.3 Hz, 1H), 6.80 (m, 1H), 6.86 (d, J = 7.8 Hz, 1H ), 7.20 (t, J = 7.8 Hz, 1H), 7.32 (dd, J = 1.8, 8.6, 7.5 Hz, 1H), 7.40-7.46 (m, 2H), 7.67 (s, 1H), 7.76 (d, J = 8.6 Hz, 1H), 7.76-7.79 (m, 2H); 13 C NMR (100 Hz, CDCl 3 ) δ 30.54, 45.90, 49.23, 54.68, 111.2, 114.0, 120.1, 125.5, 126.0, 126.4, 127.4, 127.6 , 128.2, 129.5, 132.1, 133.3, 141.0, 145.2, 160.0, 206.7; MS (m / z) 133 (51), 153 (51), 215 (33), 247 (100), 261 (30), 304 ( 82, M + ) exact mass calcd for C 21 H 20 O 2 : 304.1463; found 604.1475. [Α] 21 D (c in CHCl 3 ): -30 (0.23), 96% ee (OD-H, Hexane: iPrOH = 9/1, t r = 39, 41)

光学活性β−ジアリールカルボニル化合物として、以下の表２に記載した各生成物５ｍ〜５ｐを製造した。生成物５ｍ〜５ｐの反応式、反応条件、反応の手順は実施例１と同様である。 As optically active β-diarylcarbonyl compounds, the products 5m to 5p described in Table 2 below were produced. The reaction formulas, reaction conditions, and reaction procedures for the products 5m to 5p are the same as in Example 1.

生成物５ｂ〜５ｌの反応に用いた基質とアリールボロン酸を表２に示す。
Table 2 shows the substrates and arylboronic acids used in the reaction of products 5b-5l.

各生成物５ｍ〜５ｐについての分析結果を以下に示す。 生成物：(S)-4-(4-メトキシフェニル)-4-フェニル-2-ブタノン(5m) HPLC column, DAICEL CHIRALCEL OD-H: eluent, n-hexane/2-propanol (9:1): flow rate, 0.5 mL/min: tR 18 and 20 min; IR(neat);700, 838, 1250, 1506, 1605, 1720, 2940, 2960 cm-1; 1HNMR(400 MHz, CDCl3) δ 2.04 (s, 3H), 3.13 (d, J = 7.6 Hz, 2H), 3.73 (s, 3H), 4.53 (t, J = 7.6 Hz 1H), 6.95 (d, J = 6.6 Hz, 1H), 7.11-7.29 (m, 7H); 13CNMR(100 Hz, CDCl3) δ 30.05, 38.7, 45.2, 49.8, 55.1, 113.9, 126.3, 127.5, 128.5, 128.6, 135.9, 144.2, 158.0, 206.8; MS(m/z) 254 (M+); [α]22 D(c in CHCl3): +0.75 (0.60) The analysis result about each product 5m-5p is shown below. Product: (S) -4- (4-Methoxyphenyl) -4-phenyl-2-butanone (5m) HPLC column, DAICEL CHIRALCEL OD-H: eluent, n-hexane / 2-propanol (9: 1): flow rate, 0.5 mL / min: t R 18 and 20 min; IR (neat); 700, 838, 1250, 1506, 1605, 1720, 2940, 2960 cm -1 ; 1 HNMR (400 MHz, CDCl3) δ 2.04 ( s, 3H), 3.13 (d, J = 7.6 Hz, 2H), 3.73 (s, 3H), 4.53 (t, J = 7.6 Hz 1H), 6.95 (d, J = 6.6 Hz, 1H), 7.11-7.29 (m, 7H); 13 C NMR (100 Hz, CDCl 3 ) δ 30.05, 38.7, 45.2, 49.8, 55.1, 113.9, 126.3, 127.5, 128.5, 128.6, 135.9, 144.2, 158.0, 206.8; MS (m / z) 254 (M + ); [α] 22 D (c in CHCl 3 ): +0.75 (0.60)

生成物：(S)-4-(3,4-ジメトキシフェニル)-4-フェニル-2-ブタノン(5n) HPLC column, DAICEL CHIRALCEL OD-H: eluent, n-hexane/2-propanol (9:1): flow rate, 0.5 mL/min: tR 23 and 27 min; IR(neat, cm-1): 1712, 1512, 1235, 1141, 1024, 700; 1HNMR(400 Hz, CDCl3) δ 7.87(d, J = 8.3 Hz, 2H), 7.33-7.17(m, 7H), 4.65(t, J = 7.3 Hz, 1H), 3.21(d, J = 7.3 Hz, 2H), 2.55(s, 3H), 2.10 (s, 3H); 13CNMR(400 Hz, CDCl3) δ 206.1, 197.5, 149.4, 142.9, 135.3, 128.7, 128.6, 127.9, 127.6, 126.7, 49.0, 45.7, 30.5, 26.4; MS(m/z) 103(10), 227(100), 284(39, M+); exact mass calcd for C18H20O3: 284.1412; found 284.1407; [α]23 D(c in CHCl3): -1.7(0.59), 97%ee (OD-H, Hexane:iPrOH=9/1, tr=23, 27) Product: (S) -4- (3,4-dimethoxyphenyl) -4-phenyl-2-butanone (5n) HPLC column, DAICEL CHIRALCEL OD-H: eluent, n-hexane / 2-propanol (9: 1 ): flow rate, 0.5 mL / min: t R 23 and 27 min; IR (neat, cm -1 ): 1712, 1512, 1235, 1141, 1024, 700; 1 HNMR (400 Hz, CDCl 3 ) δ 7.87 ( d, J = 8.3 Hz, 2H), 7.33-7.17 (m, 7H), 4.65 (t, J = 7.3 Hz, 1H), 3.21 (d, J = 7.3 Hz, 2H), 2.55 (s, 3H), 2.10 (s, 3H); 13 CNMR (400 Hz, CDCl 3 ) δ 206.1, 197.5, 149.4, 142.9, 135.3, 128.7, 128.6, 127.9, 127.6, 126.7, 49.0, 45.7, 30.5, 26.4; MS (m / z ) 103 (10), 227 (100), 284 (39, M + ); exact mass calcd for C 18 H 20 O 3 : 284.1412; found 284.1407; [α] 23 D (c in CHCl 3 ): -1.7 ( 0.59), 97% ee (OD -H, Hexane: iPrOH = 9/1, t r = 23, 27)

生成物：(S)-4-(3,4-メチレンジオキシフェニル)-4-フェニル-2-ブタノン(5o) HPLC column, DAICEL CHIRALCEL OD-H: eluent, n-hexane/2-propanol (9:1): flow rate, 0.5 mL/min: tR 21 and 26 min; IR(neat, cm-1): 1486, 1230, 1036, 699, 533; 1HNMR(400 Hz, CDCl3) δ 7.31-7.17(m, 5H), 6.74-6.70(m, 3H), 5.91(s, 2H), 4.52(t, J = 7.6 Hz, 1H), 3.14(d, J = 7.3 Hz, 2H), 2.10(s, 3H); 13CNMR(400 Hz, CDCl3) δ 206.7, 147.7, 146.0, 143.9, 137.8, 128.6, 127.5, 126.5, 120.5, 108.2, 108.1, 100.9, 49.7, 45.7, 30.6; MS(m/z) 77(4.8), 152(22), 211(100), 225(3.2), 268(44, M+); exact mass calcd for C17H16O3: 268.1099; found 268.1101; [α]23 D(c in CHCl3): +1.8(0.41), 95%ee (OD-H, Hexane:iPrOH=9/1, tr=21, 26) Product: (S) -4- (3,4-methylenedioxyphenyl) -4-phenyl-2-butanone (5o) HPLC column, DAICEL CHIRALCEL OD-H: eluent, n-hexane / 2-propanol (9 : 1): flow rate, 0.5 mL / min: t R 21 and 26 min; IR (neat, cm -1 ): 1486, 1230, 1036, 699, 533; 1 HNMR (400 Hz, CDCl 3 ) δ 7.31- 7.17 (m, 5H), 6.74-6.70 (m, 3H), 5.91 (s, 2H), 4.52 (t, J = 7.6 Hz, 1H), 3.14 (d, J = 7.3 Hz, 2H), 2.10 (s , 3H); 13 C NMR (400 Hz, CDCl 3 ) δ 206.7, 147.7, 146.0, 143.9, 137.8, 128.6, 127.5, 126.5, 120.5, 108.2, 108.1, 100.9, 49.7, 45.7, 30.6; MS (m / z) 77 (4.8), 152 (22), 211 (100), 225 (3.2), 268 (44, M + ); exact mass calcd for C 17 H 16 O 3 : 268.1099; found 268.1101; [α] 23 D ( c in CHCl 3): +1.8 ( 0.41), 95% ee (OD-H, Hexane: iPrOH = 9/1, t r = 21, 26)

(S)-4-(4-アセトキシフェニル)-4-フェニル-2-ブタノン(5p) HPLC column, DAICEL CHIRALCEL OD-H: eluent, n-hexane/2-propanol (9:1): flow rate, 0.5 mL/min: tR 31 and 37 min;IR(neat, cm-1): 1714, 1677, 1603, 1357, 1266, 700, 596, 539; 1HNMR(400 Hz, CDCl3) δ 7.87(d, J = 8.3 Hz, 2H), 7.33-7.17(m, 7H), 4.65(t, J = 7.3 Hz, 1H), 3.21(d, J = 7.3 Hz, 2H), 2.55(s, 3H), 2.10 (s, 3H); 13CNMR(400 Hz, CDCl3) δ 206.1, 197.5, 149.4, 142.9, 135.3, 128.7, 128.6, 127.9, 127.6, 126.7, 49.0, 45.7, 30.5, 26.4; MS(m/z) 77(8), 165(30), 209(49), 223(39), 266(58, M+); exact mass calcd for C18H18O2: 266.1307; found 266.1309; [α]23 D(c in CHCl3): +15.7(0.34), 93%ee (OD-H, Hexane:iPrOH=9/1, tr=31, 37) (S) -4- (4-acetoxyphenyl) -4-phenyl-2-butanone (5p) HPLC column, DAICEL CHIRALCEL OD-H: eluent, n-hexane / 2-propanol (9: 1): flow rate, 0.5 mL / min: t R 31 and 37 min; IR (neat, cm -1 ): 1714, 1677, 1603, 1357, 1266, 700, 596, 539; 1 HNMR (400 Hz, CDCl 3 ) δ 7.87 (d , J = 8.3 Hz, 2H), 7.33-7.17 (m, 7H), 4.65 (t, J = 7.3 Hz, 1H), 3.21 (d, J = 7.3 Hz, 2H), 2.55 (s, 3H), 2.10 (s, 3H); 13 C NMR (400 Hz, CDCl 3 ) δ 206.1, 197.5, 149.4, 142.9, 135.3, 128.7, 128.6, 127.9, 127.6, 126.7, 49.0, 45.7, 30.5, 26.4; MS (m / z) 77 (8), 165 (30), 209 (49), 223 (39), 266 (58, M + ); exact mass calcd for C 18 H 18 O 2 : 266.1307; found 266.1309; [α] 23 D ( c in CHCl 3): +15.7 ( 0.34), 93% ee (OD-H, Hexane: iPrOH = 9/1, t r = 31, 37)

光学活性β−ジアリールカルボニル化合物として、以下の表３に記載した各生成物６ａ〜６ｈを製造した。生成物６（６ａ〜６ｈ）の反応式Xを以下に示す。
As optically active β-diarylcarbonyl compounds, the products 6a to 6h described in Table 3 below were produced. Reaction formula X of product 6 (6a-6h) is shown below.

(+)-6-メトキシ-2-メチル-4-フェニル-4H-クロメン(6a)の合成 窒素雰囲気、アセトン (1 ml)と水 (0.1 ml)中で、ビス（ベンゾニトリル）（(2S, 3S)-(-)-ビス(ジフェニルホスフィノ)ブタン）パラジウムヘキサフルオロアンチモン酸塩 [Pd((S, S)-chiraphos)(PhCN)2]SbF6（0.01 mmol, 1 mol%）に対し、α,β-不飽和-β-アリールカルボニル化合物(0.5 mmol)と、ボロン酸 (0.6 mmol)を加え20度で21時間攪拌した。反応液にエーテルを加え、飽和塩化アンモニウム水溶液で有機層を洗浄した。有機層に無水硫酸マグネシウムを加え乾燥後、ろ過し減圧濃縮し残渣をシリカゲルクロマトグラフィー（ヘキサン：酢酸エチル＝３０：１〜１５：１）で精製し、6-メトキシ-2-メチル−4−フェニル−2−クロマノール(A)を得た(133.8mg, 99%)。続いて得られたクロマノール誘導体(A, 0.5 mmol)をトルエン (4 ml)中、p-トルエンスルホン酸 (10 mol％)を加え、モレキューシーブス4A (1g) 存在下、3時間加熱還流した。室温まで冷却後、反応液にエーテルを加え、飽和塩化アン
モニウム水溶液で有機層を洗浄した。有機層に無水硫酸マグネシウムを加え乾燥後、ろ過、減圧濃縮し残渣をシリカゲルクロマトグラフィー（ヘキサン：酢酸エチル＝３０：１）で精製し、表３の6-メトキシ-2-メチル-4-フェニル-4H-クロメンを生成物として得た(117.4mg, 94%)。 Synthesis of (+)-6-methoxy-2-methyl-4-phenyl-4H-chromene (6a) In a nitrogen atmosphere, acetone (1 ml) and water (0.1 ml), bis (benzonitrile) ((2S, 3S)-(-)-Bis (diphenylphosphino) butane) palladium hexafluoroantimonate [Pd ((S, S) -chiraphos) (PhCN) 2 ] SbF 6 (0.01 mmol, 1 mol%) An α, β-unsaturated-β-arylcarbonyl compound (0.5 mmol) and boronic acid (0.6 mmol) were added, and the mixture was stirred at 20 degrees for 21 hours. Ether was added to the reaction solution, and the organic layer was washed with a saturated aqueous ammonium chloride solution. Anhydrous magnesium sulfate was added to the organic layer, dried, filtered, concentrated under reduced pressure, and the residue was purified by silica gel chromatography (hexane: ethyl acetate = 30: 1-15: 1) to give 6-methoxy-2-methyl-4-phenyl. -2-Chromanol (A) was obtained (133.8 mg, 99%). Subsequently, the obtained chromanol derivative (A, 0.5 mmol) was added with p-toluenesulfonic acid (10 mol%) in toluene (4 ml), and heated to reflux for 3 hours in the presence of Molecule 4S (1 g). After cooling to room temperature, ether was added to the reaction solution, and the organic layer was washed with a saturated aqueous ammonium chloride solution. Anhydrous magnesium sulfate was added to the organic layer, dried, filtered, and concentrated under reduced pressure. The residue was purified by silica gel chromatography (hexane: ethyl acetate = 30: 1), and 6-methoxy-2-methyl-4-phenyl- 4H-chromene was obtained as product (117.4 mg, 94%).

生成物の分析結果を以下に示す。キラルHPLC（DAICEL CHIRALCEL OD-H）を用い、溶媒としてヘキサン：イソプロピルアルコール＝99.5：0.5を用いて流速0.5ml/minで流し、生成物を測定したところ、二つの鏡像異性体の溶出時間は15分と18分であった。これより、生成物の鏡像異性体過剰率(%ee)を95%eeと同定した。 HPLC column, DAICEL CHIRALPAK AD-H: eluent, n-hexane/2-propanol (99.5:0.5): flow rate, 0.5 mL/min: tR 15 and 18 min; IR(neat, cm-1): 1696, 1490, 1215, 1030, 942, 820, 697; 1HNMR(400 Hz, CDCl3) δ 7.30-7.16(m, 5H), 6.88 (d, J = 8.8 Hz, 1H), 6.68 (dd, J = 2.9, 9.2 Hz, 1H), 6.41 (d, J = 2.9 Hz, 1H), 4.72-4.71(m, 1H), 4.60(brs, 1H), 3.64 (s, 3H), 1.93 (s, 3H); 13CNMR(400 Hz, CDCl3) δ 155.1, 147.0, 146.9, 145.2, 128.5, 128.0, 126.4, 123.6, 117.0, 113.9, 113.4, 99.5, 55.4, 41.3, 19.3; MS(m/z) 77(50), 105(43), 150(40), 175(100), 228(86), 237 (40), 252 (40, M+); exact mass calcd for C17H16O2: 252.1150; found 252.1155; [α]21 D(c in CHCl3): +172.3(0.53), 96%ee (AD-H, Hexane:iPrOH=99.5/0.5, tr=15, 18) The analysis results of the product are shown below. Using chiral HPLC (DAICEL CHIRALCEL OD-H), hexane: isopropyl alcohol = 99.5: 0.5 as a solvent and flowing at a flow rate of 0.5 ml / min, the product was measured. The elution time of the two enantiomers was 15 Minutes and 18 minutes. From this, the enantiomeric excess (% ee) of the product was identified as 95% ee. HPLC column, DAICEL CHIRALPAK AD-H: eluent, n-hexane / 2-propanol (99.5: 0.5): flow rate, 0.5 mL / min: t R 15 and 18 min; IR (neat, cm -1 ): 1696, 1490, 1215, 1030, 942, 820, 697; 1 HNMR (400 Hz, CDCl 3 ) δ 7.30-7.16 (m, 5H), 6.88 (d, J = 8.8 Hz, 1H), 6.68 (dd, J = 2.9 , 9.2 Hz, 1H), 6.41 (d, J = 2.9 Hz, 1H), 4.72-4.71 (m, 1H), 4.60 (brs, 1H), 3.64 (s, 3H), 1.93 (s, 3H); 13 CNMR (400 Hz, CDCl 3 ) δ 155.1, 147.0, 146.9, 145.2, 128.5, 128.0, 126.4, 123.6, 117.0, 113.9, 113.4, 99.5, 55.4, 41.3, 19.3; MS (m / z) 77 (50), 105 (43), 150 (40), 175 (100), 228 (86), 237 (40), 252 (40, M + ); exact mass calcd for C 17 H 16 O 2 : 252.1150; found 252.1155; [ α] 21 D (c in CHCl 3): +172.3 (0.53), 96% ee (AD-H, Hexane: iPrOH = 99.5 / 0.5, t r = 15, 18)

以下、式Xと同様にして、表３に示す基質とアリールボロン酸を用いて生成物６ｂ〜６ｈを得た。
Thereafter, in the same manner as in Formula X, products 6b to 6h were obtained using the substrates shown in Table 3 and arylboronic acid.

各生成物６ｂ〜６ｈについての分析結果を以下に示す。 生成物：(+)-2,4-ジフェニル-4H-クロメン(6b) HPLC column, DAICEL CHIRALPAK AD-H: eluent, n-hexane/2-propanol (99.5:0.5): flow rate, 0.5 mL/min: tR 15 and 20 min; IR(neat, cm-1): 1696, 1482, 1439, 1240, 1219, 1173, 1037, 927, 809; 1HNMR(400 Hz, CDCl3) δ 7.72(d, J = 1.8, 8.6 Hz, 2H), 7.42-7.10(m, 10H), 6.97-6.95(m, 2H), 5.59(d, J = 4.1 Hz, 1H), 4.84(d, J = 4.1 Hz, 1H); 13CNMR(400 Hz, CDCl3) δ 150.9, 147.7, 146.6, 134.1, 129.7, 128.6, 128.4, 128.34, 128.30, 127.6, 126.6, 124.7, 123.4, 123.2, 116.6, 100.8, 41.1; MS(m/z) 178(15), 207(100), 284(35, M+); exact mass calcd for C21H16O: 284.1201; found 284.1201; [α]21 D(c in CHCl3): +31.2(0.61), 99%ee (AD-H, Hexane:iPrOH=99.5/0.5, tr=15, 20) The analysis result about each product 6b-6h is shown below. Product: (+)-2,4-Diphenyl-4H-chromene (6b) HPLC column, DAICEL CHIRALPAK AD-H: eluent, n-hexane / 2-propanol (99.5: 0.5): flow rate, 0.5 mL / min : t R 15 and 20 min; IR (neat, cm -1 ): 1696, 1482, 1439, 1240, 1219, 1173, 1037, 927, 809; 1 HNMR (400 Hz, CDCl 3 ) δ 7.72 (d, J = 1.8, 8.6 Hz, 2H), 7.42-7.10 (m, 10H), 6.97-6.95 (m, 2H), 5.59 (d, J = 4.1 Hz, 1H), 4.84 (d, J = 4.1 Hz, 1H) ; 13 CNMR (400 Hz, CDCl 3 ) δ 150.9, 147.7, 146.6, 134.1, 129.7, 128.6, 128.4, 128.34, 128.30, 127.6, 126.6, 124.7, 123.4, 123.2, 116.6, 100.8, 41.1; MS (m / z ) 178 (15), 207 (100), 284 (35, M + ); exact mass calcd for C 21 H 16 O: 284.1201; found 284.1201; [α] 21 D (c in CHCl 3 ): +31.2 (0.61 ), 99% ee (AD- H, Hexane: iPrOH = 99.5 / 0.5, t r = 15, 20)

生成物： (+)-4-(4-メトキシフェニル)-2,6-ジメチル-4H-クロメン(6c) HPLC column, DAICEL CHIRALPAK AD-H: eluent, n-hexane/2-propanol (99.5:0.5): flow rate, 0.5 mL/min: tR 16 and 17 min; IR(neat, cm-1): 1697, 1497, 1315, 1245, 1219, 1171, 1034, 812, 531; 1HNMR(400 Hz, CDCl3) δ 7.15(d, J = 8.3 Hz, 2H), 6.91 (dd, J = 1.4, 7.8 Hz, 1H), 6.86-6.81(m, 3H), 6.70(brs, 1H), 4.73-4.72(m, 1H), 4.54(brs, 1H), 3.78(s, 3H), 2.17(s, 3H), 1.94(s, 3H); 13CNMR(400 Hz, CDCl3) δ 158.0, 148.8, 146.6, 139.7, 132.2, 129.9, 129.0, 128.0, 122.9, 115.9, 113.8, 100.5, 55.1, 40.0, 20.5, 19.3; MS(m/z) 159(81), 251(100), 266(62, M+); exact mass calcd for C18H18O2: 266.1307; found 266.1298; [α]21 D(c in CHCl3): +145.5(0.70), 97%ee (AD-H, Hexane:iPrOH=99.5/0.5, tr=16, 17) Product: (+)-4- (4-Methoxyphenyl) -2,6-dimethyl-4H-chromene (6c) HPLC column, DAICEL CHIRALPAK AD-H: eluent, n-hexane / 2-propanol (99.5: 0.5 ): flow rate, 0.5 mL / min: t R 16 and 17 min; IR (neat, cm -1 ): 1697, 1497, 1315, 1245, 1219, 1171, 1034, 812, 531; 1 HNMR (400 Hz, CDCl 3 ) δ 7.15 (d, J = 8.3 Hz, 2H), 6.91 (dd, J = 1.4, 7.8 Hz, 1H), 6.86-6.81 (m, 3H), 6.70 (brs, 1H), 4.73-4.72 ( m, 1H), 4.54 (brs, 1H), 3.78 (s, 3H), 2.17 (s, 3H), 1.94 (s, 3H); 13 CNMR (400 Hz, CDCl 3 ) δ 158.0, 148.8, 146.6, 139.7 , 132.2, 129.9, 129.0, 128.0, 122.9, 115.9, 113.8, 100.5, 55.1, 40.0, 20.5, 19.3; MS (m / z) 159 (81), 251 (100), 266 (62, M + ); exact mass calcd for C 18 H 18 O 2 : 266.1307; found 266.1298; [α] 21 D (c in CHCl 3 ): +145.5 (0.70), 97% ee (AD-H, Hexane: iPrOH = 99.5 / 0.5, t r = 16, 17)

生成物：(+)-4-(3-メトキシフェニル)-2,6-ジメチル-4H-クロメン(6d) HPLC column, DAICEL CHIRALPAK AD-H: eluent, n-hexane/2-propanol (99.5:0.5): flow rate, 0.5 mL/min: tR 13 and 16 min; IR(neat, cm-1): 1696, 1597, 1485, 1311, 1257, 1238, 1219, 1179, 1044, 813, 699; 1HNMR(400 Hz, CDCl3) δ 7.22(t, J = 7.8 Hz, 1H), 6.91 (dd, J = 1.9, 8.3 Hz, 1H), 6.84-6.72(m, 5H), 4.74-4.73(m, 1H), 4.56(brs, 1H), 3.78(s, 3H), 2.17(s, 3H), 1.94(s, 3H); 13CNMR(400 Hz, CDCl3) δ 159.7, 149.0, 148.9, 146.9, 132.3, 129.9, 129.4, 128.2, 122.4, 120.6, 116.0, 114.2, 111.3, 100.1, 55.1, 40.9, 20.6, 19.3; MS(m/z) 159(100), 251(37), 266(34, M+); exact mass calcd for C18H18O2: 266.1307; found 266.1307; [α]21 D(c in CHCl3): +181.9(0.67), 97%ee (OD-H, Hexane:iPrOH=99.5/0.5, tr=13, 16) Product: (+)-4- (3-methoxyphenyl) -2,6-dimethyl-4H-chromene (6d) HPLC column, DAICEL CHIRALPAK AD-H: eluent, n-hexane / 2-propanol (99.5: 0.5 ): flow rate, 0.5 mL / min: t R 13 and 16 min; IR (neat, cm -1 ): 1696, 1597, 1485, 1311, 1257, 1238, 1219, 1179, 1044, 813, 699; 1 HNMR (400 Hz, CDCl 3 ) δ 7.22 (t, J = 7.8 Hz, 1H), 6.91 (dd, J = 1.9, 8.3 Hz, 1H), 6.84-6.72 (m, 5H), 4.74-4.73 (m, 1H ), 4.56 (brs, 1H), 3.78 (s, 3H), 2.17 (s, 3H), 1.94 (s, 3H); 13 C NMR (400 Hz, CDCl 3 ) δ 159.7, 149.0, 148.9, 146.9, 132.3, 129.9, 129.4, 128.2, 122.4, 120.6, 116.0, 114.2, 111.3, 100.1, 55.1, 40.9, 20.6, 19.3; MS (m / z) 159 (100), 251 (37), 266 (34, M + ); exact mass calcd for C 18 H 18 O 2 : 266.1307; found 266.1307; [α] 21 D (c in CHCl 3 ): +181.9 (0.67), 97% ee (OD-H, Hexane: iPrOH = 99.5 / 0.5, (t r = 13, 16)

生成物：(+)-2,6-ジメチル-4-(3,4-メチレンジオキシフェニル)-4H-クロメン(6e) HPLC column, DAICEL CHIRALPAK AD-H: eluent, n-hexane/2-propanol (99.5:0.5): flow rate, 0.5 mL/min: tR 12 and 17 min; IR(neat, cm-1): 1696, 1482, 1439, 1240, 1219, 1173, 1037, 927, 809; 1HNMR(400 Hz, CDCl3) δ 6.91-6.89(m, 1H), 6.81(d, J = 8.3 Hz, 1H), 6.73-6.70(m, 2H), 6.69(d, J = 8.3 Hz, 2H), 5.90(dd, J = 1.5, 4.9 Hz, 2H), 4.71-4.70(m, 1H), 4.50(brs, 1H), 2.17(s, 3H), 1.93(s, 3H); 13CNMR(400 Hz, CDCl3) δ 148.8, 147.8, 146.8, 146.0, 141.6, 132.3, 129.8, 128.1, 122.6, 120.7, 116.0, 108.7, 107.8, 100.8, 100.2, 40.5, 20.5, 19.3; MS(m/z) 159(100), 265(61), 280(62, M+); exact mass calcd for C18H16O3: 280.1099; found 280.1098; [α]21 D(c in CHCl3): +184.9(0.72), 98%ee (AD-H, Hexane:iPrOH=99.5/0.5, tr=12, 17) Product: (+)-2,6-Dimethyl-4- (3,4-methylenedioxyphenyl) -4H-chromene (6e) HPLC column, DAICEL CHIRALPAK AD-H: eluent, n-hexane / 2-propanol (99.5: 0.5): flow rate, 0.5 mL / min: t R 12 and 17 min; IR (neat, cm -1 ): 1696, 1482, 1439, 1240, 1219, 1173, 1037, 927, 809; 1 HNMR (400 Hz, CDCl 3 ) δ 6.91-6.89 (m, 1H), 6.81 (d, J = 8.3 Hz, 1H), 6.73-6.70 (m, 2H), 6.69 (d, J = 8.3 Hz, 2H), 5.90 (dd, J = 1.5, 4.9 Hz, 2H), 4.71-4.70 (m, 1H), 4.50 (brs, 1H), 2.17 (s, 3H), 1.93 (s, 3H); 13 CNMR (400 Hz, CDCl 3 ) δ 148.8, 147.8, 146.8, 146.0, 141.6, 132.3, 129.8, 128.1, 122.6, 120.7, 116.0, 108.7, 107.8, 100.8, 100.2, 40.5, 20.5, 19.3; MS (m / z) 159 (100) , 265 (61), 280 (62, M + ); exact mass calcd for C 18 H 16 O 3 : 280.1099; found 280.1098; [α] 21 D (c in CHCl 3 ): +184.9 (0.72), 98% ee (AD-H, Hexane: iPrOH = 99.5 / 0.5, t r = 12, 17)

生成物：(+)-2,6-ジメチル-4-(4-メチルフェニル)-4H-クロメン(6f) HPLC column, DAICEL CHIRALCEL OD-H: eluent, n-hexane/2-propanol (99.5:0.5): flow rate, 0.5 mL/min: tR 114 and 119 min; IR(neat, cm-1): 1697, 1495, 1315, 1219, 1168, 811; 1HNMR(400 Hz, CDCl3) δ 7.10(s, 4H), 6.90-6.81(m, 2H), 6.69(s, 1H), 4.72-4.71(m, 1H), 4.54(brs, 1H), 2.30(s, 3H), 2.15(s, 3H), 1.92(s, 3H); 13CNMR(400 Hz, CDCl3) δ 148.9, 146.7, 144.5, 135.8, 132.3, 129.9, 129.2, 128.1, 128.0, 122.8, 115.9, 100.5, 40.5, 20.9, 20.6, 19.3; MS(m/z) 77(11), 91(27), 119(20), 134(21), 159(100), 178(26), 195(35), 211(46), 235(67), 250(34, M+); exact mass calcd for C18H18O: 250.1358; found 250.1362; [α]21 D(c in CHCl3): +119.8(0.74), 97%ee (OD-H, Hexane:iPrOH=99.5/0.5, tr=114, 119) Product: (+)-2,6-Dimethyl-4- (4-methylphenyl) -4H-chromene (6f) HPLC column, DAICEL CHIRALCEL OD-H: eluent, n-hexane / 2-propanol (99.5: 0.5 ): flow rate, 0.5 mL / min: t R 114 and 119 min; IR (neat, cm -1 ): 1697, 1495, 1315, 1219, 1168, 811; 1 HNMR (400 Hz, CDCl 3 ) δ 7.10 ( s, 4H), 6.90-6.81 (m, 2H), 6.69 (s, 1H), 4.72-4.71 (m, 1H), 4.54 (brs, 1H), 2.30 (s, 3H), 2.15 (s, 3H) , 1.92 (s, 3H); 13 C NMR (400 Hz, CDCl 3 ) δ 148.9, 146.7, 144.5, 135.8, 132.3, 129.9, 129.2, 128.1, 128.0, 122.8, 115.9, 100.5, 40.5, 20.9, 20.6, 19.3; MS (m / z) 77 (11), 91 (27), 119 (20), 134 (21), 159 (100), 178 (26), 195 (35), 211 (46), 235 (67) , 250 (34, M + ); exact mass calcd for C 18 H 18 O: 250.1358; found 250.1362; [α] 21 D (c in CHCl 3 ): +119.8 (0.74), 97% ee (OD-H, Hexane: iPrOH = 99.5 / 0.5, t r = 114, 119)

生成物：(+)-2,6-ジメチル-4-フェニル-4H-クロメン(6g) HPLC column, DAICEL CHIRALCEL OD-H: eluent, n-hexane/2-propanol (99.5:0.5): flow rate, 0.5 mL/min: tR 9.2 and 10 min; IR(neat, cm-1): 1696, 1494, 1314, 1217, 942, 813, 697, 531; 1HNMR(400 Hz, CDCl3) δ 7.31-7.17(m, 5H), 6.91(dd, , J = 2.4, 8.2 Hz, 1H), 6.83 (d, J = 8.2 Hz, 1H), 6.69(s, 1H), 4.73(dd, J =1.0, 3.0 Hz, 1H), 4.58(s, 1H), 2.16(s, 3H), 1.93(s, 1H); 13CNMR(400 Hz, CDCl3) δ 148.9, 147.3, 146.8, 132.3, 129.9, 128.5, 128.18, 128.17, 126.3, 122.6, 116.0, 100.2, 40.9, 20.6, 19.3; MS(m/z) 159(100), 221(31), 236(25, M+); exact mass calcd for C17H16O: 236.1201; found 236.1206; [α]21 D(c in CHCl3): +142.4(0.70), 96%ee (OD-H, Hexane:iPrOH=99.5/0.5, tr=9.2, 10) Product: (+)-2,6-Dimethyl-4-phenyl-4H-chromene (6g) HPLC column, DAICEL CHIRALCEL OD-H: eluent, n-hexane / 2-propanol (99.5: 0.5): flow rate, 0.5 mL / min: t R 9.2 and 10 min; IR (neat, cm -1 ): 1696, 1494, 1314, 1217, 942, 813, 697, 531; 1 HNMR (400 Hz, CDCl 3 ) δ 7.31-7.17 (m, 5H), 6.91 (dd,, J = 2.4, 8.2 Hz, 1H), 6.83 (d, J = 8.2 Hz, 1H), 6.69 (s, 1H), 4.73 (dd, J = 1.0, 3.0 Hz , 1H), 4.58 (s, 1H), 2.16 (s, 3H), 1.93 (s, 1H); 13 C NMR (400 Hz, CDCl 3 ) δ 148.9, 147.3, 146.8, 132.3, 129.9, 128.5, 128.18, 128.17 , 126.3, 122.6, 116.0, 100.2, 40.9, 20.6, 19.3; MS (m / z) 159 (100), 221 (31), 236 (25, M + ); exact mass calcd for C 17 H 16 O: 236.1201 ; found 236.1206; [α] 21 D (c in CHCl 3): +142.4 (0.70), 96% ee (OD-H, Hexane: iPrOH = 99.5 / 0.5, t r = 9.2, 10)

生成物：(+)-2,6-ジメチル-4-(4-アセトキシフェニル)-4H-クロメン(6h) HPLC column, DAICEL CHIRALPAK AD-H: eluent, n-hexane/2-propanol (15:1): flow rate, 0.5 mL/min: tR 12 and 15 min; IR(neat, cm-1): 1680, 1603, 1495, 1315, 1265, 1219, 1169, 943, 813, 597; 1HNMR(400 Hz, CDCl3) δ 7.90(d, J = 8.3 Hz, 2H), 7.31(d, J = 8.3 Hz, 2H), 6.92(dd, d, J = 1.5, 8.3 Hz, 1H), 6.85(d, J = 8.3 Hz, 1H), 6.64(brs, 1H), 4.72-4.71 (m, 1H), 4.66 (brs, 1H), 2.57(s, 3H), 2.16(s, 3H), 1.95(s, 3H); 13CNMR(400 Hz, CDCl3) δ 197.7, 152.5, 148.8, 147.4, 135.4, 132.5, 129.7, 129.0, 128.7, 128.5, 128.4, 128.3, 121.1, 116.1, 99.3, 40.9, 26.5, 20.5, 19.3; MS(m/z) 159(100), 263(28), 278(19, M+); exact mass calcd for C19H18O2: 278.1307; found 278.1316; [α]21 D(c in CHCl3): +263.9(0.72), 96%ee (AD-H, Hexane:iPrOH=15/1, tr=12, 15) Product: (+)-2,6-Dimethyl-4- (4-acetoxyphenyl) -4H-chromene (6h) HPLC column, DAICEL CHIRALPAK AD-H: eluent, n-hexane / 2-propanol (15: 1 ): flow rate, 0.5 mL / min: t R 12 and 15 min; IR (neat, cm -1 ): 1680, 1603, 1495, 1315, 1265, 1219, 1169, 943, 813, 597; 1 HNMR (400 Hz, CDCl 3 ) δ 7.90 (d, J = 8.3 Hz, 2H), 7.31 (d, J = 8.3 Hz, 2H), 6.92 (dd, d, J = 1.5, 8.3 Hz, 1H), 6.85 (d, J = 8.3 Hz, 1H), 6.64 (brs, 1H), 4.72-4.71 (m, 1H), 4.66 (brs, 1H), 2.57 (s, 3H), 2.16 (s, 3H), 1.95 (s, 3H ); 13 CNMR (400 Hz, CDCl 3 ) δ 197.7, 152.5, 148.8, 147.4, 135.4, 132.5, 129.7, 129.0, 128.7, 128.5, 128.4, 128.3, 121.1, 116.1, 99.3, 40.9, 26.5, 20.5, 19.3; MS (m / z) 159 (100), 263 (28), 278 (19, M + ); exact mass calcd for C 19 H 18 O 2 : 278.1307; found 278.1316; [α] 21 D (c in CHCl 3 ): +263.9 (0.72), 96 % ee (AD-H, Hexane: iPrOH = 15/1, t r = 12, 15)

Claims (2)

一般式（VI）
（式VI中、R１,R２はそれぞれ同一又は異なっていても良い水素又はアルキル基を表し、R3は水素、アルキル基、又は置換若しくは無置換のアリール基を表し、R4は塩素原子、フッ素原子、ヒドロキシ基、炭素数１から８のアルキル基、炭素数１から８のアルキル基を有していてもよいフェニル基、炭素数２から８のアルケニル基、炭素数２から８のアルキニル基、炭素数１から８のアルコキシ基、炭素数１から８のアルキルチオ基、シアノ基、ホルミル基、炭素数２から８のアシル基、炭素数１から８のアルキル基を有していてもよいベンゾイル基、炭素数２から８のアルコキシカルボニル基、炭素数１から８のアルキル基を有していてもよいフェノキシカルボニル基、炭素数１から８のアルキル基を有していてもよいアミノ基、炭素数１から８のアルキル基を有していてもよいカルバモイル基、ニトロ基、炭素数１から８のフルオロアルキル基、又は炭素数１から８のアルキル基を有していてもよいフェノキシ基を表す。）で表されるα,β-不飽和-β-アリールカルボニル化合物と、
一般式（II）Ar2-BXmMnで表されるアリールボロン酸若しくはその誘導体、又は一般式（III）
（式II及びIII中、Ar２は置換または無置換のアリール基を表し、Xは水酸基、アルコキシ基、又はフッ素原子を示し、mは1から3の整数であり、Mはアルカリ金属であり、nは０または１の整数である。）で表されるアリールボロン酸無水物とを、
一般式（IV）PdYoL1 p(Chiraphos)q(式IV中、YはClO4、BF4、PF6、SbF6、OTf、ハロゲン原子、ヒドロキシ基、アルコキシ基、アシルオキシ基を表し、L１は有機配位子、L２は光学活性ホスフィン配位子を示す。o,p,qはそれぞれ０から６の整数を表す。)で表されるパラジウム錯体触媒の存在下で反応させ、
一般式（VII）
(式VII中、Ar１、Ar2、R1,R2,R3及びR4はそれぞれ式II〜Vに用いた置換基と同一である)で表されるクロマノール誘導体（VII）を製造することを特徴とする光学活性化合物の製造方法。 General formula (VI)
(In Formula VI, R 1 and R 2 each represent hydrogen or an alkyl group which may be the same or different, R 3 represents hydrogen, an alkyl group, or a substituted or unsubstituted aryl group, and R 4 represents a chlorine atom. , Fluorine atom, hydroxy group, alkyl group having 1 to 8 carbon atoms, phenyl group optionally having 1 to 8 carbon atoms, alkenyl group having 2 to 8 carbon atoms, alkynyl having 2 to 8 carbon atoms Group, an alkoxy group having 1 to 8 carbon atoms, an alkylthio group having 1 to 8 carbon atoms, a cyano group, a formyl group, an acyl group having 2 to 8 carbon atoms, and an alkyl group having 1 to 8 carbon atoms. A benzoyl group, an alkoxycarbonyl group having 2 to 8 carbon atoms, a phenoxycarbonyl group optionally having an alkyl group having 1 to 8 carbon atoms, an amino group optionally having an alkyl group having 1 to 8 carbon atoms, 1 carbon A carbamoyl group optionally having 8 alkyl groups, a nitro group, a fluoroalkyl group having 1 to 8 carbon atoms, or a phenoxy group optionally having an alkyl group having 1 to 8 carbon atoms. An α, β-unsaturated-β-arylcarbonyl compound represented by:
Arylboronic acid represented by general formula (II) Ar 2 -BX m Mn or a derivative thereof, or general formula (III)
(In formulas II and III, Ar 2 represents a substituted or unsubstituted aryl group, X represents a hydroxyl group, an alkoxy group, or a fluorine atom, m is an integer of 1 to 3, M is an alkali metal, n is an integer of 0 or 1.)
General formula (IV) PdY o L 1 p (Chiraphos) q (wherein Y represents ClO 4 , BF 4 , PF 6 , SbF 6 , OTf, halogen atom, hydroxy group, alkoxy group, acyloxy group, L 1 represents an organic ligand, L 2 represents an optically active phosphine ligand, and o, p, and q each represents an integer of 0 to 6.) In the presence of a palladium complex catalyst represented by
Formula (VII)
(In formula VII, Ar 1 , Ar 2 , R 1 , R 2 , R 3 and R 4 are the same as the substituents used in formulas II to V, respectively) to produce a chromanol derivative (VII) A method for producing an optically active compound. 反応系に銀塩を加えることを特徴とする請求項１に記載の光学活性化合物の製造方法。 The method for producing an optically active compound according to claim 1, wherein a silver salt is added to the reaction system.
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