Chiral Amplification through Organocatalytic Photochirogenesis with Higher-Order Supramolecular Complex

• Project/Area Number: 26620030
• Research Category: Grant-in-Aid for Challenging Exploratory Research
• Allocation Type: Multi-year Fund
• Research Field: Organic chemistry
• Research Institution: Osaka University
• Principal Investigator: INOUE Yoshihisa 大阪大学, 工学(系)研究科(研究院), 教授 (30112543)
• Co-Investigator(Kenkyū-buntansha): 森 直 大阪大学, 大学院工学研究科 (70311769) ; 福原 学 大阪大学, 大学院工学研究科 (30505996) ; 西嶋 政樹 大阪大学, 産学連携本部 (70448017)
• Project Period (FY): 2014-04-01 – 2015-03-31
• Project Status: Completed (Fiscal Year 2014)
• Budget Amount: ¥3,900,000 (Direct Cost: ¥3,000,000、Indirect Cost: ¥900,000); Fiscal Year 2014: ¥3,900,000 (Direct Cost: ¥3,000,000、Indirect Cost: ¥900,000)
• Keywords: 光化学 / 超分子化学 / 触媒的不斉合成 / 不斉増殖 / 高次錯体 / 水素結合 / 不斉合成

Outline of Final Research Achievements

Photochirogenesis has rapidly developed in recent years as an alternative methodology to complement the conventional asymmetric syntheses using chiral catalysts and enzymes. In the present study, we have achieved the simultaneous enhancement of reactivity and stereoselectivity in an enantiodifferentiating photocyclodimerization of 2-anthracenecarboxylic acid through the formation of a novel higher-order (2:2) complexation with L-prolinol, which was shown to be expandable to a wider range of photosubstrates with carboxylic acid moiety/ies. This enabled us to accomplish the organocatalytic supramolecular photochirogenesis for the first time, which is inherently difficult and hence has never been achieved in asymmetric synthesis mediated by a chiral template.

Research Products

• [Journal Article] Catalytic Supramolecular Photochirogenesis (2015)
  • Author(s): Z. Yan, W. Wu, C. Yang and Y. Inoue
  • Journal Title: Supramolecular Catalysis Volume: 2
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Ammonia-Driven Chirality Inversion and Enhancement in Enantiodifferentiating Photocyclodimerization of 2-Anthracenecarboxylate Mediated by Diguanidino-γ-cyclodextrin. (2014)
  • Author(s): Yao, J.; Yan, Z.; Ji, J.; Wu, W.; Yang, C.; Nishijima, M.; Fukuhara, G.; Mori, T.; Inoue, Y.
  • Journal Title: Journal of the American Chemical Society Volume: 136 Issue: 19 Pages: 6916-6919
  • DOI: 10.1021/ja5032908
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Mammalian serum albumins as a chiral mediator library for bio-supramolecular photochirogenesis: optimizing enantiodifferentiating photocyclodimerization of 2-anthracenecarboxylate. (2014)
  • Author(s): Nishijima, M.; Goto, M.; Fujikawa, M.; Yang, C.; Mori, T.; Wada, T.; Inoue, Y.
  • Journal Title: Chem. Commun. Volume: 50 Issue: 91 Pages: 14082-14085
  • DOI: 10.1039/c4cc04818k
  • Peer Reviewed / Acknowledgement Compliant