Degradative Functionalizations of Heteroarenes by Precisely Designed Catalysts

• Project Area: Precise Formation of a Catalyst Having a Specified Field for Use in Extremely Difficult Substrate Conversion Reactions
• Project/Area Number: 16H01019
• Research Category: Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: Kyoto University
• Principal Investigator: 依光 英樹 京都大学, 理学研究科, 教授 (00372566)
• Project Period (FY): 2016-04-01 – 2018-03-31
• Project Status: Completed (Fiscal Year 2017)
• Budget Amount: ¥5,720,000 (Direct Cost: ¥4,400,000、Indirect Cost: ¥1,320,000); Fiscal Year 2017: ¥2,860,000 (Direct Cost: ¥2,200,000、Indirect Cost: ¥660,000); Fiscal Year 2016: ¥2,860,000 (Direct Cost: ¥2,200,000、Indirect Cost: ¥660,000)
• Keywords: マンガン触媒 / ホウ素 / アート錯体 / ベンゾフラン / ジベンゾチオフェン / ヘテロ芳香環 / 遷移金属触媒 / ホウ素挿入 / アザボリン

Outline of Annual Research Achievements

マンガン触媒を用いたベンゾフランの開環ジリチオ化とヘテロ原子挿入：マンガン触媒存在下ベンゾフランに対し過剰量の有機リチウム反応剤を作用させるとフラン骨格のC-O結合が切断され、開環ジリチオ化が効率よく進行することを見いだした。また、生成したジリチオ化体に対し各種ヘテロ求電子剤を作用させることで、対応するヘテロ環化合物を合成することにも成功した。本手法は同一の出発原料からケイ素やホウ素など様々なヘテロ元素を含む環状化合物を与える、多様性指向型芳香環メタモルフォシスであり、ケミカルスペースの拡張に繋がる意義深い研究である。
ロジウム/銅共触媒系を利用したジベンゾチオフェンの開環ジボリル化を経由する芳香環メタモルフォシス：多様性指向型芳香環メタモルフォシスの新たな方法論として、開環ジボリル化を経るジベンゾチオフェンの変換法に着目した。まず、ジベンゾチオフェンの開環ジボリル化の反応条件を探索した。ロジウムホスフィン/銅NHC共触媒とフッ化セシウム存在下、ビスピナコラートジボロンをジベンゾチオフェンに対し作用させたところ、対応する開環ジボリル化体が得られた。生成したジボリルビフェニルは、期待した通り様々な環状化合物へ容易に変換可能であった。例えば、パラジウム触媒存在下においてgem-ジブロモアルケンを反応させると、対応するフルベン誘導体が収率よく得られた。一方、一当量の過酸化水素を作用させると、二つのホウ素原子のうち一方のみが酸化され、対応するジベンゾオキサボリンが選択的に得られた。同様にO-アリールヒドロキシルアミンを作用させると、炭素-ホウ素結合の酸化的アミノ化が進行し、ジベンゾアザボリンが得られた。

Research Progress Status

29年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

29年度が最終年度であるため、記入しない。

Research Products

• [Int'l Joint Research] Yonsei University(韓国)
• [Journal Article] Palladium-Catalyzed Amination of Aryl Sulfoxides (2018)
  • Author(s): Yuto Yoshida, Shinya Otsuka, Keisuke Nogi, and Hideki Yorimitsu
  • Journal Title: Org. Lett. Volume: 20 Issue: 4 Pages: 1134-1137
  • DOI: 10.1021/acs.orglett.8b00060
  • NAID: 120006406842
  • Peer Reviewed
• [Journal Article] Palladium-Catalyzed Borylation of Aryl Sulfoniums with Diborons (2018)
  • Author(s): Hiroko Minami, Shinya Otsuka, Keisuke Nogi, and Hideki Yorimitsu
  • Journal Title: ACS Catal. Volume: 8 Issue: 1 Pages: 579-583
  • DOI: 10.1021/acscatal.7b03841
  • Peer Reviewed
• [Journal Article] Palladium-Catalyzed Arylation of Benzylic C-H Bonds of Azaarylmethanes with Aryl Sulfides (2017)
  • Author(s): Ke Gao, Keita Yamamoto, Keisuke Nogi, and Hideki Yorimitsu
  • Journal Title: Synlett Volume: 28 Issue: 20 Pages: 2956-2960
  • DOI: 10.1055/s-0036-1589098
  • Peer Reviewed
• [Journal Article] C-S Bond Alkynylation of Diaryl Sulfoxides with Terminal Alkynes by Means of a Palladium-NHC Catalyst (2017)
  • Author(s): Yuto Yoshida, Keisuke Nogi, and Hideki Yorimitsu
  • Journal Title: Synlett Volume: 28 Issue: 19 Pages: 2561-2564
  • DOI: 10.1055/s-0036-1591676
  • Peer Reviewed
• [Journal Article] Nickel-Catalyzed Cross-Coupling Reaction of Aryl Sulfoxides with Arylzinc Reagents: When the Leaving Group is an Oxidant (2017)
  • Author(s): Keita Yamamoto, Shinya Otsuka, Keisuke Nogi, and Hideki Yorimitsu
  • Journal Title: ACS Catal. Volume: 7 Issue: 11 Pages: 7623-7628
  • DOI: 10.1021/acscatal.7b02347
  • Peer Reviewed
• [Journal Article] Manganese-Catalyzed Ring Opening of Benzofurans and Its Application to Insertion of Heteroatoms into the C2-O Bond (2017)
  • Author(s): Shun Tsuchiya, Hayate Saito, Keisuke Nogi, and Hideki Yorimitsu
  • Journal Title: Org. Lett. Volume: 19 Issue: 20 Pages: 5557-5560
  • DOI: 10.1021/acs.orglett.7b02660
  • Peer Reviewed
• [Journal Article] Robust Palladium-Catalyzed Arylation of Catalyst-Poisoning ortho-Sulfanyl Aryl Halides with Tetraarylborates and Its Application to Synthesis of π-Extended Dibenzothiophenes (2017)
  • Author(s): Dhananjayan Vasu, Jan Niklas Hausmann, Hayate Saito, Tomoyuki Yanagi, Hideki Yorimitsu, and Atsuhiro Osuka
  • Journal Title: Asian J. Org. Chem. Volume: 6 Issue: 10 Pages: 1390-1393
  • DOI: 10.1002/ajoc.201700323
  • Peer Reviewed
• [Journal Article] Rh/Cu-cocatalyzed Ring-opening Diborylation of Dibenzothiophenes for Aromatic Metamorphosis via Diborylbiaryls (2017)
  • Author(s): Hayate Saito, Keisuke Nogi, and Hideki Yorimitsu
  • Journal Title: Chemistry Letters Volume: 46 Issue: 8 Pages: 1122-1125
  • DOI: 10.1246/cl.170415
  • NAID: 130005907027
  • ISSN: 0366-7022, 1348-0715
  • Peer Reviewed / Open Access
• [Journal Article] Palladium-Catalyzed Double Borylation of Diaryl Sulfoxides with Diboron (2017)
  • Author(s): Hayate Saito, Keisuke Nogi, and Hideki Yorimitsu
  • Journal Title: Synthesis Volume: 49 Issue: 21 Pages: 4769-4774
  • DOI: 10.1055/s-0036-1588848
  • Peer Reviewed
• [Journal Article] Aromatic metamorphosis: conversion of an aromatic skeleton into a different ring system (2017)
  • Author(s): Keisuke Nogi and Hideki Yorimitsu
  • Journal Title: Chem. Commun. Volume: 53 Issue: 29 Pages: 4055-4065
  • DOI: 10.1039/c7cc00078b
  • Peer Reviewed
• [Journal Article] Aromatic Metamorphosis of Dibenzofurans into Triphenylenes Starting with Nickel-Catalyzed Ring-Opening C-O Arylation (2017)
  • Author(s): Kurata, Y.; Otsuka, S.; Fukui, N.; Nogi, K.; Yorimitsu, H.; Osuka, A.
  • Journal Title: Org. Lett. Volume: 19 Issue: 6 Pages: 1274-1277
  • DOI: 10.1021/acs.orglett.6b03861
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Synthesis of Dibenzophospholes from Dibenzothiophene Dioxides and Phenylphosphine by Twofold SNAr Reactions (2017)
  • Author(s): Onoda, M.; Koyanagi, Y.; Saito, H.; Bhanuchandra, M.; Matano, Y.; Yorimitsu, H.
  • Journal Title: Asian J. Org. Chem. Volume: 6 Issue: 3 Pages: 257-261
  • DOI: 10.1002/ajoc.201600612
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Base-Free Palladium-Catalyzed Hydrodechlorination of Aryl Chlorides with Pinacol Borane (2017)
  • Author(s): Yamamoto, Y.; Nogi, K.; Yorimitsu, H.; Osuka, A.
  • Journal Title: ChemistrySelect Volume: 2 Issue: 4 Pages: 1723-1727
  • DOI: 10.1002/slct.201700189
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Nickel-Catalyzed Boron Insertion into the C2-O Bond of Benzofurans (2016)
  • Author(s): Saito, H.; Otsuka, S.; Nogi, K.; Yorimitsu, H.
  • Journal Title: J. Am. Chem. Soc. Volume: 138 Issue: 47 Pages: 15315-15318
  • DOI: 10.1021/jacs.6b10255
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Metal-Free Approach to Biaryls from Phenols and Aryl Sulfoxides by Temporarily Sulfur-Tethered Regioselective C-H/C-H Coupling (2016)
  • Author(s): Yanagi, T.; Otsuka, S.; Kasuga, Y.; Fujimoto, K.; Murakami, K.; Nogi, K.; Yorimitsu, H.; Osuka, A.
  • Journal Title: J. Am. Chem. Soc. Volume: 138 Issue: 44 Pages: 14582-14585
  • DOI: 10.1021/jacs.6b10278
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Pictet-Spengler Synthesis of Quinoline-Fused Porphyrins and Phenanthroline-Fused Diporphyrins (2016)
  • Author(s): Gao, K.; Fukui, N.; Jung, S. I.; Yorimitsu, H.; Kim, D.; Osuka, A.
  • Journal Title: Angew. Chem. Int. Ed. Volume: 55 Issue: 42 Pages: 13038-13042
  • DOI: 10.1002/anie.201606293
  • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] Pd-NHC-Catalyzed Alkynylation of General Aryl Sulfides with Alkynyl Grignard Reagents (2016)
  • Author(s): Baralle, A.; Yorimitsu, H.; Osuka, A.
  • Journal Title: Chem. Eur. J. Volume: 22 Issue: 31 Pages: 10768-10772
  • DOI: 10.1002/chem.201602315
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Base-Free Palladium-Catalyzed Borylation of Aryl Chlorides with Diborons (2016)
  • Author(s): Yamamoto, Y.; Matsubara, H.; Yorimitsu, H.; Osuka, A.
  • Journal Title: ChemCatChem Volume: 8 Issue: 14 Pages: 2317-2320
  • DOI: 10.1002/cctc.201600456
  • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] Palladium-Catalyzed ipso-Borylation of Aryl Sulfides with Diborons (2016)
  • Author(s): Bhanuchandra, M.; Baralle, A.; Otsuka, S.; Nogi, K.; Yorimitsu, H.; Osuka, A.
  • Journal Title: Org. Lett. Volume: 18 Issue: 12 Pages: 2966-2969
  • DOI: 10.1021/acs.orglett.6b01305
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Cross-coupling of Aryl Sulfides Powered by <i><b>N</b></i>-Heterocyclic Carbene Ligands (2016)
  • Author(s): Gao, K.; Otsuka, S.; Baralle, A.; Nogi, K.; Yorimitsu, H.; Osuka, A.
  • Journal Title: Journal of Synthetic Organic Chemistry, Japan Volume: 74 Issue: 11 Pages: 1119-1127
  • DOI: 10.5059/yukigoseikyokaishi.74.1119
  • NAID: 130005433319
  • ISSN: 0037-9980, 1883-6526
  • Peer Reviewed / Acknowledgement Compliant
• [Presentation] ロジウム触媒によるジベンゾチオフェン類の開環ジボリル化反応 (2017)
  • Author(s): 齊藤颯, 大塚慎也, 野木馨介, 依光英樹
  • Organizer: 日本化学会第97春季年会
  • Place of Presentation: 慶應義塾大学（横浜市）
  • Year and Date: 2017-03-16
• [Presentation] Catalytic C-S Bond Cleavage Exploiting the Potential of Organosulfur Chemistry (2017)
  • Author(s): Hideki Yorimitsu
  • Organizer: Basel Chemical Society Symposium
  • Int'l Joint Research / Invited
• [Presentation] Aromatic Metamorphosis by Means of Catalytic Cleavage of Endocyclic Bonds (2017)
  • Author(s): Hideki Yorimitsu
  • Organizer: Perspectives on Organometallics in Organic Synthesis
  • Int'l Joint Research / Invited
• [Presentation] A Journey from Catalytic C-S Bond Activation to Aromatic Metamorphosis (2017)
  • Author(s): Hideki Yorimitsu
  • Organizer: Nordic/Kyoto OMCOS 2017
  • Int'l Joint Research / Invited
• [Presentation] Aromatic Metamorphosis: Conversion of a Heteroaromatic Skeleton into a Different Ring System (2017)
  • Author(s): Hideki Yorimitsu
  • Organizer: Japanese-Spanish Symposium on Modern Synthetic Methodology
  • Int'l Joint Research / Invited
• [Presentation] 炭素－硫黄結合の触媒的変換から芳香環メタモーフォシスへの展開 (2017)
  • Author(s): 依光英樹
  • Organizer: 第45回オルガノメタリックセミナー
  • Invited
• [Presentation] 芳香族性の破壊を伴う分子変換 (2017)
  • Author(s): 依光英樹
  • Organizer: 産業総合研究所触媒化学融合研究センター第49回講演会
  • Invited
• [Presentation] Aromatic Metamorphosis: Conversions of Heteroaromatic Skeletons into Different Rings (2017)
  • Author(s): Hideki Yorimitsu
  • Organizer: 8th International Collaborative and Cooperative Chemistry Symposium
  • Int'l Joint Research / Invited
• [Presentation] Aromatic Metamorphosis of Benzofurans (2016)
  • Author(s): Saito, H.; Kurata, Y.; Otsuka, S.; Nogi, K.; Yorimitsu, H.
  • Organizer: Catalysis and Fine Chemicals 2016
  • Place of Presentation: Taipei
  • Year and Date: 2016-11-11
  • Int'l Joint Research / Invited
• [Presentation] Nickel-catalyzed Boron Insertion into the C2-O Bond of Benzofurans (2016)
  • Author(s): Saito, H.; Otsuka, S.; Yorimitsu, H.
  • Organizer: International Symposium on C-O Activation
  • Place of Presentation: Himeji
  • Year and Date: 2016-10-25
  • Int'l Joint Research
• [Presentation] Aromatic Metamorphosis of Benzofurans (2016)
  • Author(s): Yorimitsu, H.
  • Organizer: International Symposium on C-O Activation
  • Place of Presentation: Himeji
  • Year and Date: 2016-10-25
  • Int'l Joint Research / Invited
• [Presentation] ニッケル触媒によるベンゾフラン類の2位炭素-酸素結合へのホウ素挿入：オキサボリニンを経由した骨格改変 (2016)
  • Author(s): 齊藤颯, 大塚慎也, 依光英樹
  • Organizer: 第63回有機金属化学討論会
  • Place of Presentation: 早稲田大学
  • Year and Date: 2016-09-14
• [Presentation] ニッケル触媒によるベンゾフラン類の2位炭素-酸素結合へのホウ素挿入：オキサボリニンを経由した骨格改変 (2016)
  • Author(s): 齊藤颯, 大塚慎也, 依光英樹
  • Organizer: 第33回有機合成化学セミナー
  • Place of Presentation: ヒルトンニセコビレッジ（北海道）
  • Year and Date: 2016-09-06
• [Presentation] Nickel-catalyzed Boron Insertion into the C2-O Bond of Benzofurans: Skeletal Transformations of Furan Ring via Oxaborinine (2016)
  • Author(s): Saito, H.; Otsuka, S.; Yorimitsu, H.
  • Organizer: 20th International Symposium on Homogeneous Catalysis
  • Place of Presentation: Kyoto
  • Year and Date: 2016-07-10
  • Int'l Joint Research
• [Presentation] Aromatic Metamorphosis of Benzofurans (2016)
  • Author(s): Kurata, Y.; Saito, H.; Otsuka, S.; Yorimitsu, H.
  • Organizer: The 12th International Symposium on Organic Reactions
  • Place of Presentation: Kyoto
  • Year and Date: 2016-04-22
  • Int'l Joint Research / Invited
• [Remarks] 京都大学 大学院理学研究科 化学専攻 有機化学研究室
  • URL: http://kuchem.kyoto-u.ac.jp/orgchem/
• [Remarks] 研究室HP
  • URL: http://kuchem.kyoto-u.ac.jp/orgchem/