Catalytic reactions via metalacyclization with a nitrone group

2015 Fiscal Year Final Research Report

• Project/Area Number: 26620022
• Research Category: Grant-in-Aid for Challenging Exploratory Research
• Allocation Type: Multi-year Fund
• Research Field: Organic chemistry
• Research Institution: Tohoku University
• Principal Investigator: Nakamura Itaru 東北大学, 理学(系)研究科(研究院), 准教授 (00333899)
• Project Period (FY): 2014-04-01 – 2016-03-31
• Keywords: ロジウム触媒 / ヘテロ環化合物 / カスケード反応 / 転位反応

Outline of Final Research Achievements

Eight-membered nitrogenous heterocycles (azocines) can be found in numerous naturally occurring products, such as manzamine alkaloids, grandilodines, and otonecines, as well as biologically active compounds, such as XIAP antagonists. Moreover, azocine derivatives have been utilized as synthetic intermediates in providing various alkaloids, such as loline and FR-900482. We successfully developed the effective transformation of O-propargylic oximes that possess a cyclobutyl group at the oxime moiety, in the presence of a Rh-catalyst, into the corresponding azocine oxide in good to excellent yields.　In the present reaction, the starting oxime undergoes a 2,3-rearrangement to form N-allenylnitrone intermediate, then the formation of azarhodacycle, followed by ring expansion of the strained cyclobutyl group.

Free Research Field

有機合成化学、有機金属化学