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Benzyne‐Promoted Curtius‐Type Rearrangement of Acyl Hydrazides in the Presence of Nucleophiles
Author(s) -
Guo JingYu,
Zhong ChenHao,
He ZengYang,
Tian ShiKai
Publication year - 2018
Publication title -
asian journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.846
H-Index - 44
eISSN - 2193-5815
pISSN - 2193-5807
DOI - 10.1002/ajoc.201700598
Subject(s) - chemistry , curtius rearrangement , hydrazide , nucleophile , aryne , thiophenol , trifluoromethanesulfonate , trimethylsilyl , amine gas treating , organic chemistry , moiety , acylation , medicinal chemistry , catalysis
A protocol has been developed for the Curtius‐type rearrangement of acyl hydrazides in the presence of nucleophiles by activating acyl hydrazides with benzyne to generate aminimide intermediates. A wide variety of N′ ‐methyl‐ N ′‐phenyl acyl hydrazides were treated with various alcohols in the presence of 2‐(trimethylsilyl)phenyl triflate and CsF under mild conditions to afford structurally diverse carbamates in moderate to excellent yields. Importantly, complete retention of configuration was observed in the reaction of enantioenriched α‐chiral alkanoyl hydrazides. Replacing the alcohol with water, an amine, an N′ ‐unsubstituted acyl hydrazide, an alkoxyamine, or a thiophenol in the reaction permitted facile synthesis of ureas and analogues.