Investigation on reaction mechanism in the transition state of bifunctional chiral metal nanoparticle catalysts

2017 Fiscal Year Final Research Report

• Project/Area Number: 15KT0058
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Multi-year Fund
• Section: 特設分野
• Research Field: Transition State Control
• Research Institution: The University of Tokyo
• Principal Investigator: Miyamura Hiroyuki 東京大学, 大学院理学系研究科(理学部), 助教 (00548943)
• Project Period (FY): 2015-07-10 – 2018-03-31
• Keywords: 不斉合成 / キラル金属ナノ粒子 / 遷移状態 / 反応機構研究 / 二機能性触媒 / キラル配位子 / 不斉1,4-付加反応

Outline of Final Research Achievements

Chiral metal nanoparticle catalysts of bifunctional chiral ligand and Rh-Ag nanoparticles mediate asymmetric 1,4-addition of aryl boronic acid to unsaturated carbonyl compounds in high yield and enantioselectivity. We hypothesized that the diene structure of the ligand construct asymmetric environment through interaction with active metal species and the secondary amide moiety places substrate in appropriate position in the reaction environment through hydrogen bonding. According to kinetic studies, XPS analysis, SR-MAS NMR analysis, and non-linear effect analysis provided various information about the active metal species, fashion of interaction between active metal species and chiral ligand, and transition states of intermediates in the catalytic cycles.

Free Research Field

有機合成化学