JP7341464B2 - Aromatic ring photoredox catalyst with high reducing power - Google Patents
Aromatic ring photoredox catalyst with high reducing power Download PDFInfo
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- JP7341464B2 JP7341464B2 JP2019160380A JP2019160380A JP7341464B2 JP 7341464 B2 JP7341464 B2 JP 7341464B2 JP 2019160380 A JP2019160380 A JP 2019160380A JP 2019160380 A JP2019160380 A JP 2019160380A JP 7341464 B2 JP7341464 B2 JP 7341464B2
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- 238000004519 manufacturing process Methods 0.000 claims description 10
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- NCSZRNMVUILZEC-UHFFFAOYSA-N 3-methylidene-1,2-dihydroindene Chemical compound C1=CC=C2C(=C)CCC2=C1 NCSZRNMVUILZEC-UHFFFAOYSA-N 0.000 description 1
- 125000003349 3-pyridyl group Chemical group N1=C([H])C([*])=C([H])C([H])=C1[H] 0.000 description 1
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- VWVKUNOPTJGDOB-BDHVOXNPSA-N Anhydrous tofogliflozin Chemical compound C1=CC(CC)=CC=C1CC1=CC=C(CO[C@@]23[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O3)O)C2=C1 VWVKUNOPTJGDOB-BDHVOXNPSA-N 0.000 description 1
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- 229940126279 Compound 14f Drugs 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- NAVMQTYZDKMPEU-UHFFFAOYSA-N Targretin Chemical compound CC1=CC(C(CCC2(C)C)(C)C)=C2C=C1C(=C)C1=CC=C(C(O)=O)C=C1 NAVMQTYZDKMPEU-UHFFFAOYSA-N 0.000 description 1
- QABUURICQJOWID-MRXNPFEDSA-N [5-chloro-6-[(6-methylpyridin-3-yl)amino]pyridin-3-yl]-[(2r)-2-ethylpiperidin-1-yl]methanone Chemical compound CC[C@@H]1CCCCN1C(=O)C(C=C1Cl)=CN=C1NC1=CC=C(C)N=C1 QABUURICQJOWID-MRXNPFEDSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 125000005577 anthracene group Chemical group 0.000 description 1
- XRWSZZJLZRKHHD-WVWIJVSJSA-N asunaprevir Chemical compound O=C([C@@H]1C[C@H](CN1C(=O)[C@@H](NC(=O)OC(C)(C)C)C(C)(C)C)OC1=NC=C(C2=CC=C(Cl)C=C21)OC)N[C@]1(C(=O)NS(=O)(=O)C2CC2)C[C@H]1C=C XRWSZZJLZRKHHD-WVWIJVSJSA-N 0.000 description 1
- 229960002938 bexarotene Drugs 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 229940127206 compound 14d Drugs 0.000 description 1
- 229940126208 compound 22 Drugs 0.000 description 1
- 229940125961 compound 24 Drugs 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 125000004986 diarylamino group Chemical group 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- OUBZLXSQKQMFAH-UHFFFAOYSA-N ethyl 2-(4-fluoroanilino)-2-oxoacetate Chemical compound CCOC(=O)C(=O)NC1=CC=C(F)C=C1 OUBZLXSQKQMFAH-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
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- 229910052740 iodine Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- LXNFVVDCCWUUKC-UHFFFAOYSA-N methyl 4-chlorobenzoate Chemical compound COC(=O)C1=CC=C(Cl)C=C1 LXNFVVDCCWUUKC-UHFFFAOYSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- WNOHFJIMKSDPHP-UHFFFAOYSA-N n-(2-chlorophenyl)-7-(1h-1,2,4-triazol-5-yl)benzo[c][2,6]naphthyridin-5-amine Chemical compound ClC1=CC=CC=C1NC1=NC2=C(C=3NC=NN=3)C=CC=C2C2=CN=CC=C12 WNOHFJIMKSDPHP-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000246 pyrimidin-2-yl group Chemical group [H]C1=NC(*)=NC([H])=C1[H] 0.000 description 1
- 125000004527 pyrimidin-4-yl group Chemical group N1=CN=C(C=C1)* 0.000 description 1
- 125000004528 pyrimidin-5-yl group Chemical group N1=CN=CC(=C1)* 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
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- 125000004159 quinolin-2-yl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C([H])C(*)=NC2=C1[H] 0.000 description 1
- 125000004548 quinolin-3-yl group Chemical group N1=CC(=CC2=CC=CC=C12)* 0.000 description 1
- 125000004549 quinolin-4-yl group Chemical group N1=CC=C(C2=CC=CC=C12)* 0.000 description 1
- 125000004550 quinolin-6-yl group Chemical group N1=CC=CC2=CC(=CC=C12)* 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- YAYGSLOSTXKUBW-UHFFFAOYSA-N ruthenium(2+) Chemical compound [Ru+2] YAYGSLOSTXKUBW-UHFFFAOYSA-N 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- VCZQFJFZMMALHB-UHFFFAOYSA-N tetraethylsilane Chemical compound CC[Si](CC)(CC)CC VCZQFJFZMMALHB-UHFFFAOYSA-N 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
特許法第３０条第２項適用 平成３０年９月１９日 ｈｔｔｐ：／／ｗｗｗ．ｓｈｏｋｕｂａｉ．ｏｒｇ／ｍｅｅｔｉｎｇ／ｉｎｄｅｘ．ｈｔｍｌにて発表 平成３０年９月２７日 第１２２回触媒討論会にて発表 平成３０年１０月１５日 ＮＣＴＵ－５ Ｓｔａｒ Ａｌｌｉａｎｃｅ Ｌｅｃｔｕｒｅｓ ２０１８にて発表 平成３０年１０月１７日 国立台湾大学理学院化学科松平講堂にて発表 発行者名：日本フッ素化学会 刊行物名：第４１回フッ素化学討論会要旨集 講演番号：Ｏ－１７ 発行年月日：平成３０年１０月２５日 平成３０年１０月２６日 第４１回フッ素化学討論会にて発表 平成３０年１１月１９日 特別講演会 国立大学法人徳島大学にて発表 平成３０年１１月２１日 大塚創薬化学シンポジウム２０１８にて発表 発行者名：華中師範大学、華中師範大学ｕＯｔｔａｗａ共同研究センター ■■与化学生物学教育部重点実験室 刊行物名：２０１８ ＣＣＮＵ Ｓｙｎｔｈｅｔｉｃ Ｐｈｏｔｏｃｈｅｍｉｓｔｒｙ Ｓｙｍｐｏｓｉｕｍ要旨集 発行年月日：平成３０年１１月２６日 平成３０年１１月２７日 ２０１８ ＣＣＮＵ Ｓｙｎｔｈｅｔｉｃ Ｐｈｏｔｏｃｈｅｍｉｓｔｒｙ Ｓｙｍｐｏｓｉｕｍにて発表 平成３０年１１月３０日 Ｍｉｎｉ－Ｓｙｍｐｏｓｉｕｍ ｏｎ Ｐｈｏｔｏｃｈｅｍｉｓｔｒｙにて発表 平成３０年１２月１日 学術講演 四川大学華西薬学院にて発表 平成３０年１２月３日 四川師範大学にて発表 平成３０年１２月１２日 ＩＩＴ Ｂｏｍｂａｙ Ｓｙｍｐｏｓｉｕｍ ｏｎ Ｃｈｅｍｉｃａｌ Ｓｙｎｔｈｅｓｉｓにて発表 刊行物名：Ｉｎｔｅｒｎａｔｉｏｎａｌ Ｃｏｎｆｅｒｅｎｃｅ ｏｎ Ｏｒｇａｎｏｍｅｔａｌｌｉｃｓ ａｎｄ Ｃａｔａｌｙｓｉｓ ２０１８要旨集 発行年月日：平成３０年１２月１３日 平成３０年１２月１３日 Ｉｎｔｅｒｎａｔｉｏｎａｌ Ｃｏｎｆｅｒｅｎｃｅ ｏｎ Ｏｒｇａｎｏｍｅｔａｌｌｉｃｓ ａｎｄ Ｃａｔａｌｙｓｉｓ ２０１８にて発表 平成３０年１２月１５日 パイスター分子制御による未来型物質変換研究拠点 ２０１８年度公開シンポジウムにて発表 発行者名：シンガポール国立大学、南洋理工大学、シンガポール国立化学研究所 刊行物名：１０ｔｈ Ｓｉｎｇａｐｏｒｅ Ｉｎｔｅｒｎａｔｉｏｎａｌ Ｃｈｅｍｉｓｔｒｙ Ｃｏｎｆｅｒｅｎｃｅ要旨集 発行年月日：平成３０年１２Application of Article 30, Paragraph 2 of the Patent Act September 19, 2018 http://www. Shokubai. org/meeting/index. Presented in html September 27, 2018 Presented at the 122nd Catalyst Symposium October 15, 2018 Presented at NCTU-5 Star Alliance Lectures 2018 October 17, 2018 National Taiwan University School of Science Chemistry Presented at the Matsudaira Auditorium Publisher: Japan Fluorine Chemistry Society Publication Name: Abstracts of the 41st Fluorine Chemistry Symposium Lecture Number: O-17 Date of Publication: October 25, 2018 October 2018 26th Presented at the 41st Fluorine Chemistry Symposium November 19, 2018 Special Lecture Presented at National University Corporation Tokushima University November 21, 2018 Presented at Otsuka Medicinal Chemistry Symposium 2018 Publisher: Huazhong Normal University, Huazhong Normal University uOttawa Joint Research Center Key Laboratory of Department of Chemical Biology Education Publication name: 2018 CCNU Synthetic Photochemistry Symposium Abstracts Publication date: November 26, 2018 November 2018 27th Presented at 2018 CCNU Synthetic Photochemistry Symposium November 30, 2018 Presented at Mini-Symposium on Photochemistry December 1, 2018 Academic lecture Sichuan University West China Pharmacy Presented at the hospital December 3, 2018 Sichuan Presented at Normal University December 12, 2018 Presented at IIT Bombay Symposium on Chemical Synthesis Publication name: International Conference on Organometallics and Cata lysis 2018 Abstracts Publication date: December 13, 2018 December 2018 March 13th: Presented at the International Conference on Organometallics and Catalysis 2018 December 15th, 2018: Presented at the 2018 Public Symposium of Pistar Future Materials Transformation Research Center through Molecular Control Publisher: National University of Singapore, Nanyang Technological University, singapore National Institute of Chemical Research Publication name: 10th Singapore International Chemistry Conference Abstracts Publication date: December 2018
特許法第３０条第２項適用 月１６日 平成３０年１２月１９日 １０ｔｈ Ｓｉｎｇａｐｏｒｅ Ｉｎｔｅｒｎａｔｉｏｎａｌ Ｃｈｅｍｉｓｔｒｙ Ｃｏｎｆｅｒｅｎｃｅにて発表 平成３１年１月９日 Ｔｉｔｅｃｈ Ｆｌｕｏｒｉｎｅ－Ｓｙｍｐｏｓｉｕｍにて発表 発行者名：公益社団法人 日本化学会 刊行物名：日本化学会第９９春季年会（２０１９）予稿集ＤＶＤ 講演番号：１Ｆ２－３８ 発行年月日：平成３１年３月１日 平成３１年３月１６日 日本化学会第９９春季年会（２０１９） 講演番号：１Ｆ２－３８にて発表 平成３１年４月１２日 ｈｔｔｐｓ：／／ｐｕｂｓ．ａｃｓ．ｏｒｇ／ｄｏｉ／ｐｄｆ／１０．１０２１／ａｃｓｃａｔａｌ．９ｂ００４７３？ｒａｎｄ＝ｄｓｕｙ９ｐ８ｑにて発表 発行者名：公益社団法人 日本化学会 刊行物名：日本化学会第９９春季年会（２０１９）予稿集ＤＶＤ 講演番号：１Ｆ２－４０ 発行年月日：平成３１年３月１日 平成３１年３月１６日 日本化学会第９９春季年会（２０１９） 講演番号：１Ｆ２－４０にて発表 令和１年６月１０日 テンプル大学にて発表 令和１月６月１１日 Ｏｒｇａｎｉｃ Ｃｈｅｍｉｓｔｒｙ Ｓｅｍｉｎａｒ（ペンシルベニア大学）にて発表 令和１年６月１３日 Ｏｒｇａｎｉｃ Ｃｈｅｍｉｓｔｒｙ Ｓｅｍｉｎａｒｓ（イリノイ大学 アーバナ・シャンペーン校）にて発表 令和１年６月１５日 ｈｔｔｐｓ：／／ｄｒｉｖｅ．ｇｏｏｇｌｅ．ｃｏｍ／ｆｉｌｅ／ｄ／１ＮＤＨｃｃＧ■ｓ■ＮＮ５■ＩｎＢｚｒｌｆＵ－ＨＧＶＩＰＹ３ｔＥＳ／ｖｉｅｗにて発表 令和１年６月２１日 ９ｔｈ Ｐａｃｉｆｉｃ Ｓｙｍｐｏｓｉｕｍ ｏｎ Ｒｅｄｉｃａｌ Ｃｈｅｍｉｓｔｒｙにて発表 令和１年７月５日 北海道大学電子科学研究所客員教授講演会にて発表 令和１年７月１６日 ２０１９ Ｐｈｏｔｏｃｈｅｍｉｓｔｒｙ Ｇｏｒｄｏｎ Ｒｅｓｅａｒｃｈ Ｃｏｎｆｅｒｅｎｃｅ Ｌｉｇｈｔ－Ｄｒｉｖｅｎ Ｒｅａｃｔｉｏｎｓ，Ｍａｔｅｒｉａｌｓ ａｎｄ Ｄｅｖｉｃｅｓにて発表 発行者名：山口大学 生命分子インターネットワークセンター 刊行物名：白川ＣＲＥＳＴ×ＩｏＬセンタージョイントシンポジウムブックレット 公開者：谷口 諒、納戸 直木、小池 隆司、穐田 宗隆 発行年月日：令和１年７月２９日 令和１年７月２９日 白川ＣＲＥＳＴ×ＩｏArticle 30, Paragraph 2 of the Patent Act applies December 19, 2018 Presented at the 10th Singapore International Chemistry Conference January 9, 2019 Presented at the Titech Fluorine-Symposium Publisher Name: Nippon Chemical Public Interest Incorporated Association Society Publication name: 99th Spring Annual Meeting of the Chemical Society of Japan (2019) Proceedings DVD Lecture number: 1F2-38 Publication date: March 1, 2019 March 16, 2019 99th Spring Meeting of the Chemical Society of Japan Annual meeting (2019) Lecture number: Presented at 1F2-38 April 12, 2019 https://pubs. acs. org/doi/pdf/10.1021/acscatal. 9b00473? Published on rand=dsuy9p8q Publisher name: Chemical Society of Japan Public interest incorporated association Publication name: Chemical Society of Japan 99th Spring Annual Meeting (2019) Proceedings DVD Lecture number: 1F2-40 Publication date: March 2019 March 16, 2019 Presented at the 99th Spring Annual Meeting of the Chemical Society of Japan (2019) Lecture number: 1F2-40 June 10, 2020 Presented at Temple University June 11, 2020 Presented at Organic Chemistry Seminars (University of Pennsylvania) June 13, 2020 Presented at Organic Chemistry Seminars (University of Illinois at Urbana-Champaign) June 15, 2020 https://drive. google. com/file/d/1NDHccG■NN5■InBzrlfU-HGVIPY3tES/view June 21, 2020 Presented at 9th Pacific Symposium on Redical Chemistry July 5, 2021 North Kaido University Electronic Science Research Presented at the 2019 Photochemistry Gordon Research Conference Light-Driven Reactions, Materials and Devices Publisher: Yamaguchi University Biomolecular Internetwork Center Publication name: Shirakawa CREST× IoL Center Joint Symposium Booklet Publisher: Ryo Taniguchi, Naoki Nato, Takashi Koike, Munetaka Akita Publication date: July 29, 2020 July 29, 2020 Shirakawa CREST×Io
特許法第３０条第２項適用 Ｌセンタージョイントシンポジウムにて 谷口 諒、納戸 直木、小池 隆司、穐田 宗隆が発表 発行者名：山口大学 生命分子インターネットワークセンター 刊行物名：白川ＣＲＥＳＴ×ＩｏＬセンタージョイントシンポジウムブックレット 公開者：小池 隆司 発行年月日：令和１年７月２９日 令和１年７月２９日 白川ＣＲＥＳＴ×ＩｏＬセンタージョイントシンポジウムにて小池隆司が発表Application of Article 30, Paragraph 2 of the Patent Law Ryo Taniguchi, Naoki Nato, Takashi Koike, and Munetaka Akita presented at the L Center Joint Symposium Publisher: Yamaguchi University Biomolecular Internetwork Center Publication Name: Shirakawa CREST x IoL Center Joint Symposium Booklet Publisher: Takashi Koike Publication date: July 29, 2020 July 29, 2020 Presented by Takashi Koike at the Shirakawa CREST x IoL Center joint symposium
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 novel organic molecular photoredox catalysts. 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, photoredox catalysts have attracted attention as an environmentally friendly organic synthesis tool that uses visible light as a driving force. The present inventors focused on this photoredox catalytic effect and developed a trifluoromethylation reaction of alkenes in which reduction of the trifluoromethylation reagent is the key (Y. Yasu, T. Koike, M. Akita, Angew. Chem. Int. Ed., 51, 9567, (2012)). Organic fluorine compounds are attracting attention in the medical and agrochemical fields, and the development of synthetic methods for them is important. However, conventional methods have had the problem of requiring the use of noble metals such as iridium as photocatalysts.
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 present inventors have recently discovered that perylene, a simple polycyclic aromatic hydrocarbon, acts as an effective photoredox catalyst in difluoromethylation reactions (N. Noto, T. Koike, M. Akita, Chem. Sci., 8, 6375, (2017)). Based on this result, the present inventor considered that the π-conjugated organic compound has the possibility of functioning as an excellent reduction catalyst that replaces the metal complex. On the other hand, perylene has room for improvement in terms of stability and reducing power, and furthermore, its poor solubility makes it difficult to effectively functionalize it, so its development as a catalyst has been poor. Therefore, we came up with the idea of using anthracene, which has a relatively large π-conjugated system and is easier to functionalize, as a base skeleton, and worked on developing an organic photoredox catalyst using this. As a result, they discovered that 9,10-bis(diphenylamino)anthracene (hereinafter sometimes referred to as "BDA"), in which the 9th and 10th positions of anthracene are substituted with diarylamino groups, works as an excellent reduction catalyst. (Non-patent document 1)
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。 When BDA catalyzes a fluoroalkylation reaction, there are limitations to the reactions it can be applied to, such as the need to select a cationic or highly electrophilic fluoroalkylating reagent. Against this background, the present invention aims to provide a photoredox catalyst that can be applied to a wider range of reactions.
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 intensive studies to solve the above problems, the present inventor discovered that 1,4-bis(diphenylamino)naphthalene (hereinafter referred to as "BDN"), which is a compound in which anthracene in BDA is replaced with naphthalene or benzene, ) or 1,4-bis(diphenylamino)benzene (hereinafter sometimes referred to as "BDB") has excellent catalytic activity, high reducing power, and neutral or electrophilic We found that radical generation is possible 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 catalytic mechanism from BDA (FIG. 1). That is, reactions using BDA require interaction (static quenching) between the catalyst and the substrate (Naoki Noto, Yuya Tanaka, Takashi Koike, and Munetaka Akita, ACS Catal. 2018, 8, 9408-9419 ), BDN and BDB found that such interaction is unnecessary and activation of a broader range of substrates is possible.
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)
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) General formula (I) or general formula (II) below
A photoredox catalyst characterized by containing 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 general formula (I) and general formula (II) are each independently The photoredox catalyst according to (1), which is a phenyl group optionally 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 general formula (I) and general formula (II) are each independently The photoredox catalyst according to (1), which is a phenyl group or a phenyl group substituted with a substituent at the 4th, 3rd, or 2nd position.
（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 general formula (I) and general formula (II) are each independently 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 general formula (I) and general formula (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 the compound according to (6), characterized in that:
（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) As described in (6), wherein the photoredox catalyst is a photoredox catalyst containing a compound represented by general formula (II), and the redox reaction is a dechlorination reaction of chlorobenzenes. A method for producing a compound.
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 organic fluorine compounds.
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。
The present invention will be explained in detail below.
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 naphthalen-1-yl group, or a naphthalen-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, "heteroaryl group" refers to, for example, a pyridinyl group (pyridin-2-yl group, pyridin-3-yl group, pyridin-4-yl group), pyrimidinyl group (pyrimidin-2-yl group, pyrimidin-4-yl group), 4-yl group, pyrimidin-5-yl group), furanyl group (furan-2-yl group, furan-3-yl group), thienyl group (thiophen-2-yl group, thiophen-3-yl group), quinolinyl groups (quinolin-2-yl group, quinolin-3-yl group, quinolin-4-yl group, quinolin-5-yl group, quinolin-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 "substituent" in "aryl group optionally substituted with a substituent" and "heteroaryl group optionally substituted with a substituent" refers to, for example, a halogen atom, a tert-butyl group, an aryl group, group, heteroaryl group. Further, the aryl group or heteroaryl group serving as this substituent may be further substituted with a substituent (eg, 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 only of the compound represented by general formula (I) or 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 which may be substituted with a substituent or a heteroaryl group which may be substituted with a substituent. Ar 1 , Ar 2 , Ar 3 , and Ar 4 may be any of the groups described above, but are preferably phenyl groups that may be substituted with substituents, and more preferably phenyl groups (unsubstituted phenyl ), or a phenyl group substituted with a substituent at the 4th, 3rd, or 2nd position, more preferably a phenyl group or a phenyl group substituted with a substituent at the 4th position, particularly preferably 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. Alternatively, all of Ar 1 , Ar 2 , Ar 3 , and Ar 4 may be substituted with a substituent, or only some of Ar 1 , Ar 2 , Ar 3 , and Ar 4 may be substituted with a substituent. (For example, it may be a group in which only Ar 1 and Ar 4 or only Ar 2 and Ar 3 are 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 which may be substituted with a substituent or a heteroaryl group which may be substituted with a substituent. Ar 5 , Ar 6 , Ar 7 and Ar 8 may be any of the groups described above, but are preferably a phenyl group which may be substituted with a substituent, more preferably a phenyl group or the 4-position, A phenyl group substituted with a substituent at the 3rd or 2nd position, more preferably a phenyl group or a phenyl group substituted with a substituent at the 4th position, particularly preferably a phenyl group, a 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. Alternatively, all of Ar 5 , Ar 6 , Ar 7 and Ar 8 may be substituted with a substituent, or only some of Ar 5 , Ar 6 , Ar 7 and Ar 8 may be substituted with a substituent. (For example, it may be a group in which only Ar 5 and Ar 8 are substituted with a substituent.)
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 hydrogen atoms, halogen atoms, aryl groups optionally substituted with substituents, or substituted with substituents. represents an optionally heteroaryl group. R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 may be any of the groups described above, but are preferably a hydrogen atom or a fluorine atom, and more preferably a hydrogen atom. 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 group optionally substituted with a substituent. represents a group. R 7 , R 8 , R 9 , and R 10 may be any of the groups described above, but are preferably a hydrogen atom or a fluorine atom, and more preferably a hydrogen atom. 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 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, when 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 used instead of diphenylamine as a raw material. In addition, when producing a compound having an aryl group or a heteroaryl group other than a phenyl group, a compound in which the phenyl group of diphenylamine is replaced with an aryl group or a heteroaryl group other than a 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 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, when 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 used instead of diphenylamine as a raw material. In addition, when producing a compound having an aryl group or a heteroaryl group other than a phenyl group, a compound in which the phenyl group of diphenylamine is replaced with an aryl group or a heteroaryl group other than a 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 irradiated light may be determined depending on the chemical structure of the photoredox catalyst. For example, for a photoredox catalyst containing a compound represented by general formula (I), the wavelength of the irradiated light 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 in the case of a photoredox catalyst containing a compound represented by general formula (II), the wavelength is usually in the range of 300 nm to 400 nm, preferably, The wavelength ranges from 350nm to 380nm. Furthermore, 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 is a conventionally used iridium photoredox catalyst (e.g., fac-[Ir(ppy) 3 ]) or ruthenium photoredox catalyst (e.g., [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 reactions in which the photoredox catalyst of the present invention can be used include, for example, Y. Yasu, T. Koike, M. Akita, Angew. Chem. Int. Ed., 51, 9567, (2012) Examples include reactions described in .
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。 Furthermore, as described in the Examples, the photoredox catalyst of the present invention can be used as a catalyst for the hydroxy-monofluoromethylation reaction of aromatic alkenes and the monofluoroalkylation reaction of aromatic vinyl acetate. When the photoredox catalyst of the present invention contains a compound represented by 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。 EXAMPLES Below, the present invention will be explained 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
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).
13C 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。
〔4tBu-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.
[ 4t Bu-BDN]
It is a known compound. 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).
13C 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.
〔2tBu-BDN〕
1H NMR (400 MHz, CD2Cl2, rt):δ 8.01 (dd, 3JHH = 6.5 Hz, 4JHH = 3.3 Hz, 2H; naphthalene’s Ar), 7.34 (dd, 3JHH = 6.5 Hz, 4JHH = 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, 3JHH = 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.
[ 2t 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 - 7.17 (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 ).
13C 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, 3JHH = 6.5 Hz, 4JHH = 3.3 Hz, 2H; naphthalene’s Ar), 7.35 (dd, 3JHH = 6.5 Hz, 4JHH = 3.3 Hz, 2H; naphthalene’s Ar), 7.28 (s, 2H; naphthalene’s Ar), 7.21 (t, 3JHH = 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, 1JCF = 240.9 Hz), 148.7, 144.6 (d, 4JCF = 2.5 Hz), 141.8, 132.6, 129.1 (2C), 127.4, 126.5, 124.8, 124.2 (d, 3JCF = 8.1 Hz, 2C),121.5, 121.0 (2C), 115.8 (d, 2JCF = 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).
19F 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
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 the spectrum was consistent with a previous report (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。
1H NMR (400 MHz, acetone-d6): δ 7.27 (dd, 3JHH = 7.6 Hz, 3JHH = 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, 1JCF = 241 Hz), 148.00, 144.15 (d, 4JCF = 2.6 Hz), 143.00, 129.32, 126.10 (d, 3JCF = 8.3 Hz), 125.07, 122.92, 122.36, 116.00 (d, 2JCF = 22.6 Hz).
19F NMR (376 MHz, acetone-d6): δ -121.4 (m, 2F)
1 H NMR (400 MHz, acetone-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).
13C 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).
19F 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
（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
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).
13C 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).
19F 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
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).
13C 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) ).
19F 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
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 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).
13C 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.
19F 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
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).
13C 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).
19F 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
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).
13C 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) ).
19F 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
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).
13C 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) ).
19F 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
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 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).
13C 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).
19F 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
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 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).
13C 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.
19F 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
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 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, 1H; 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).
13C 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.
19F 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
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 isomer), 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).
13C 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
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 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).
13C 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.
19F 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
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 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).
13C 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.
19F 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
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 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).
13C 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).
19F 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
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.
1H 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).
13C 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.
19F 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
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.
1H 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).
13C 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).
19F 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
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).
13C 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).
19F 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
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 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).
13C 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).
19F 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
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.
1H 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).
13C 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).
19F 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
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.
1H 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).
13C 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).
19F 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
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 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).
13C 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.
19F 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
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 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).
13C 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).
19F 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
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).
13C 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.
19F 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
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.
1H 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).
13C 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).
19F 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
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 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).
13C 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).
19F 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
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 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).
13C 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).
19F 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
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.
1H 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).
13C 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.
19F 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
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).
13C 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.
19F 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
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).
13C 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.
19F 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
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).
13C 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.
19F 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
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).
13C 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.
19F 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
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.
1H 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).
13C 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.
19F 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
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).
13C 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.
19F 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
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).
13C 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.
19F 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
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 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 ).
13C 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).
19F 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
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.
1H 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).
13C 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.
19F 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
（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。
〔実施例５〕 クロロベンゼン類の脱塩素化反応
〔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（Ered=-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 catalyst activity The activity of catalysts was compared using hydroxy-monofluoromethylation of alkenes as a probe.
Sulfoximine-type CH 2 F reagents are very difficult to reduce (E red =-2.43 V). Visible light irradiation (λ = 425 nm) of an acetone-d 6 /D 2 O mixture of 1.5 equivalents of CH 2 F reagent, p-vinylbiphenyl, and 5 mol% BDN yields the expected monofluoromethylated product. obtained (Figure 2). Several photocatalysts with strong reducing power were investigated under the same conditions. For example, fac-[Ir(ppy) 3 ], phenothiazine, 5,10-dihydrophenazine derivatives, and perylene were found to have lower activity than BDN (Figure 2). The high catalytic performance of BDN is believed to be due to its stronger reducing power as well as its visible light absorption ability and its robustness.
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。 The present invention makes it possible to efficiently synthesize organic fluorine compounds useful as medicines and agricultural chemicals, and therefore, the present invention can be used in industrial fields related to medicines and agricultural chemicals.
Claims (9)
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。 General formula (I) or general formula (II) below
A photoredox catalyst characterized by containing a compound represented by:
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| JP2000136151A (en) | 1998-10-30 | 2000-05-16 | Univ Osaka | Production of dehalogenated compound |
| JP2006182615A (en) | 2004-12-28 | 2006-07-13 | Masao Kaneko | Method of photodecomposing nitrogen-containing compound |
| JP2010229127A (en) | 2009-03-06 | 2010-10-14 | Kyushu Univ | Porphycene compound having ionic liquid-like structure and photooxidation catalyst |
| JP2014159382A (en) | 2013-02-19 | 2014-09-04 | Tokyo Institute Of Technology | Methods of producing trifluoromethyl group-containing amino compounds |
| JP2016166137A (en) | 2015-03-09 | 2016-09-15 | 国立大学法人東京工業大学 | Difluoromethyl group-containing alcohol production method |
| JP2018135274A (en) | 2017-02-20 | 2018-08-30 | Ａｇｃ株式会社 | Method of producing fluoromethyl group-containing compound using polycyclic aromatic hydrocarbon as photocatalyst |
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