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Frontispiece: Selective Synthesis of Tetrasubstituted Olefins by Copper‐Mediated Acetoxythiolation of Internal Alkynes: Scope and Mechanistic Studies
Author(s) -
Villuendas Pedro,
Ruiz Sara,
Vidossich Pietro,
Lledós Agustí,
Urriolabeitia Esteban P.
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Reports
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201885064
Subject(s) - dimer , alkyne , regioselectivity , copper , chemistry , nucleophile , olefin fiber , scope (computer science) , mechanism (biology) , medicinal chemistry , combinatorial chemistry , photochemistry , organic chemistry , catalysis , computer science , philosophy , epistemology , programming language
The dimer [Cu(OAc) 2 ] 2 promotes the addition of a thiolate and one acetate to an internal alkyne, to give a tetrasubstituted olefin in a complete stereo‐ and regioselective way. The determination of the mechanism by DFT methods shows the participation of Cu‐stabilized radical species and how the dimer accepts the two electrons released in the addition of two nucleophiles to the alkyne through a series of cooperative changes in the oxidation states of the two copper centers. The artwork, created by S. Sierra, shows the initial blue solution of copper(II) acetate, and its structure as a dimer. For more information see the Full Paper by A. Lledós, E. P. Urriolabeitia et al. on page 13124 ff.