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A Computational Study of Allene Synthesis via the ZnI 2 ‐Promoted Alleylation of Terminal Alkynes (ATA Reaction)
Author(s) -
Zhang Xue
Publication year - 2014
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.201300251
Subject(s) - allene , chemistry , hydride , alkyne , terminal (telecommunication) , combinatorial chemistry , computational chemistry , stereochemistry , catalysis , organic chemistry , metal , telecommunications , computer science
A detailed mechanism of allene formation via the ZnI 2 ‐promoted alleylation of terminal alkynes (ATA reaction) was investigated through DFT. The originally proposed pathway for this process was evaluated and accords perfectly with the calculated results. The formation of a propargylamine, the subsequent [1,5]‐hydride migration, and β‐elimination are the key steps of the whole process. The [1,5]‐hydride migration is the rate‐determining step. The main role of ZnI 2 in the whole process is alkyne activation to facilitate the [1,5]‐hydride migration and the stabilization of the zwitterionic intermediate.