Development of new visible-light-induced carbon-carbon bond formation using organosulfur compounds and its application to preparation of heteroarenes

2020 Fiscal Year Final Research Report

• Project/Area Number: 18K05121
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Review Section: Basic Section 33020:Synthetic organic chemistry-related
• Research Institution: Shizuoka University
• Principal Investigator: Sengoku Tetsuya 静岡大学, 工学部, 准教授 (70451680)
• Co-Investigator(Kenkyū-buntansha): 依田 秀実 静岡大学, 工学部, 教授 (20201072) ; 高橋 雅樹 静岡大学, 工学部, 教授 (30313935) ; 藤本 圭佑 静岡大学, 工学部, 助教 (10824542)
• Project Period (FY): 2018-04-01 – 2021-03-31
• Keywords: 有機硫黄化合物 / 可視光レドックス触媒 / 二量化 / 脱硫置換反応

Outline of Final Research Achievements

We investigated new visible-light-induced carbon-carbon bond formations using organosulfur compounds. An oxindole derivative bearing a phenylthio group underwent dehydrogenative carbon-carbon bond formation in the presence of Ru(bpy)3Cl2 under blue LEDs to give the dimeric product in 79% yield, although reactions using other α-phenylthio-carbonyl compounds resulted in no formation of the desired product.
Meanwhile, aryl benzyl sulfones underwent desulfonylative carbon-carbon bond formation with a 4-benzyl dihydropyridine derivative in the presence of a catalytic amount of Ir(ppy)3 and a stoichiometric amount of base under blue LEDs, affording bibenzyl derivatives in good yields. In addition, 3-phenyloxindole derivatives bearing a phenylsulfonyl functionality reacted with the dihydropyridine derivative under the comparable reaction conditions, undergoing desulfonative benzylation in moderate yields.

Free Research Field

有機化学

Academic Significance and Societal Importance of the Research Achievements

硫黄官能基の脱離を伴う炭素－炭素結合形成反応の開発において見出した反応では、ベンジル誘導体およびオキシインドール誘導体の両者において全炭素置換４級炭素骨格の構築に成功している。この骨格は生物活性天然物等の合成において鍵となるものであり、今後の不斉反応への展開により合成困難な天然物の不斉合成への利用が期待される。