Generalization of neighboring group participation onto non-carbon cation

2016 Fiscal Year Final Research Report

• Project/Area Number: 15K14927
• Research Category: Grant-in-Aid for Challenging Exploratory Research
• Allocation Type: Multi-year Fund
• Research Field: Chemical pharmacy
• Research Institution: The University of Tokyo
• Principal Investigator: Ohwada Tomohiko 東京大学, 大学院薬学系研究科(薬学部), 教授 (20177025)
• Research Collaborator: NING Yingtang ; FUKUDA Tomoya ; OTANI Yuko ; IKEDA Hirotaka ; KAWAHATA Masatoshi ; YAMAGUCHI Kentaro
• Project Period (FY): 2015-04-01 – 2017-03-31
• Keywords: 隣接基関与 / 窒素カチオン / 転位反応

Outline of Final Research Achievements

Neighboring group participation is defined as the action of a substituent to stabilize a transition state or intermediate by forming a bond or partial bond to the reaction center. In addition to the primary interaction with the nearest neighboring group, secondary interactions involving another neighboring group(s) could also occur in principle. We revisited this issue by showing the influence of secondary interactions on the stability and reactivity of the putative iminylium cation intermediates, formed by N-O bond cleavage of 1-tetralone oxime systems. Direct observation of the peri-bromo-iminylium intermediate in solution supported the involvement of iminylium cations and the stabilizing effect of secondary interactions arising from a distal tandem substituent.

Free Research Field

有機化学