Novel Development of an Amide Insertion Reaction and an Elucidation of metallic Property of Carbenoid Species

2017 Fiscal Year Final Research Report

• Project/Area Number: 16K18840
• Research Category: Grant-in-Aid for Young Scientists (B)
• Allocation Type: Multi-year Fund
• Research Field: Chemical pharmacy
• Research Institution: Chiba University
• Principal Investigator: Harada Shingo 千葉大学, 大学院薬学研究院, 助教 (50722691)
• Co-Investigator(Renkei-kenkyūsha): NEMOTO Tetsuhiro 千葉大学, 大学院薬学研究院, 教授 (80361450)
• Project Period (FY): 2016-04-01 – 2018-03-31
• Keywords: 金属カルベノイド / 銀 / ロジウム / 銅 / アミド / ナイトレン / 環化 / キラル

Outline of Final Research Achievements

An amide insertion reaction for the synthesis of nitrogen-bridged polycyclic frameworks was developed using a sustainable copper catalyst as an advantageous alternative to precious rhodium catalysts. The remarkable feature of this methodology is the amount of catalyst loading (0.05 mol%).
We examined the reactivity difference using the corresponding Rh nitrenoid and Rh carbenoid precursors. Computational analysis suggests that the origin of the discrepancy is the electrophilicity of the coordinating atoms to the Rh complex.
We developed asymmetric dearomatization of phenols using Ag carbenoids. The Ag catalyst promoted intramolecular dearomatization of phenols, whereas a Rh or Cu catalyst caused C-H insertion and a Buchner reaction. Studies indicated Ag carbenoids have a carbocation-like character, making their behavior and properties unique. We achieved a Ag carbenoid-mediated chemo- and highly enantioselective phenol dearomatization for the first time.

Free Research Field

化学系薬学