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One‐Pot Alkynylation of Azaaryl Aldehydes and Spontaneous Base‐Free Rearrangement into Enone Esters: an Autoinductive Mechanism
Author(s) -
Sieng Bora,
Maldonado Matias Funes,
Romagnoli Carlo,
Amedjkouh Mohamed
Publication year - 2018
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201701566
Subject(s) - chemistry , enone , deprotonation , autocatalysis , base (topology) , alcohol , mechanism (biology) , organic chemistry , stereochemistry , medicinal chemistry , catalysis , ion , mathematical analysis , philosophy , mathematics , epistemology
A direct synthesis of γ‐oxo‐α,β‐unsaturated esters has been developed. When heteroaromatic aldehydes are reacted with deprotonated ethyl propiolate, in the presence of Me 2 Zn or BuLi, the newly formed propargylic alcohol rearranged spontaneously to give the corresponding unsaturated keto ester. Isotope labeling, allenol intermediate trapping and crossover experiments provided insight into the reactive sequence and suggest an autocatalytic mechanism.