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Sequential 1,4‐/1,2‐Addition of Lithium(trimethylsilyl)diazomethane onto Cyclic Enones to Induce C−C Fragmentation and N−Li Insertion
Author(s) -
O'Connor Matthew J.,
Sun Chunrui,
Guan Xinyu,
Sabbasani Venkata R.,
Lee Daesung
Publication year - 2016
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201510152
Subject(s) - diazomethane , chemistry , trimethylsilyl , nucleophile , reagent , lithium (medication) , carbene , methylene , medicinal chemistry , reactivity (psychology) , addition reaction , nucleophilic addition , lithium diisopropylamide , fragmentation (computing) , organic chemistry , ion , catalysis , alternative medicine , pathology , deprotonation , endocrinology , computer science , operating system , medicine
α,β‐Unsaturated ketones generally undergo addition reactions with nucleophiles with a preference for either 1,2‐ or 1,4‐addition, but rarely both. However, the right combination of reagents allows for consecutive 1,4‐ and 1,2‐additions to occur: Cyclic α,β‐unsaturated ketones undergo double additions with lithium(trimethylsilyl)diazomethane, effectively generating various molecular frameworks with complexity and diversity. Owing to the sequential generation of several intermediates of multifaceted reactivity, including diazoalkane derivatives and alkylidene carbenes, it is possible to induce novel Grob‐type C−C fragmentations, alkylidene carbene mediated Li−N insertions, and dipolar cycloadditions by controlling the reaction parameters.