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The Outer‐Sphere Mechanism of Nitrene Transfer onto Gold(I) Alkyne Complexes
Author(s) -
Costa Ismael,
MarínLuna Marta,
Comesaña Marta González,
Faza Olalla Nieto,
Silva López Carlos
Publication year - 2016
Publication title -
chemcatchem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.497
H-Index - 106
eISSN - 1867-3899
pISSN - 1867-3880
DOI - 10.1002/cctc.201600354
Subject(s) - nitrene , alkyne , diazo , chemistry , moiety , photochemistry , imine , synthon , catalysis , combinatorial chemistry , stereochemistry , organic chemistry
The recently developed nitrene transfer reaction onto gold‐activated alkynes provides a route to safe and accessible synthons of α‐diazo imides. This reaction is rather unique in that it requires Au I in catalytic amounts; however, this promiscuous metal is only used to activate the alkyne moiety. After such activation is obtained, the nitrene‐transfer process occurs through an outer‐sphere mechanism, in which the metal acts only as a spectator. Density functional theory was applied to elucidate this peculiar reaction and to provide a mechanistic explanation for the experimentally observed isomers at the double bond and imine sites.