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Stereoselective Csp 3 –Csp 2 Bond‐Forming Reactions by Transition‐Metal‐Free Reductive Coupling of Cyclic Tosylhydrazones with Boronic Acids
Author(s) -
Plaza Manuel,
PérezAguilar M. Carmen,
Valdés Carlos
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201600837
Subject(s) - stereoselectivity , chemistry , cyclohexanone , stereochemistry , computational chemistry , organic chemistry , catalysis
The reactions between alkenylboronic acids and tosylhydrazones derived from substituted cyclohexanones lead to the construction of disubstituted cyclohexanes with total regio‐ and stereoselectivity. In these transition‐metal‐free processes, a Csp 3 −Csp 2 and Csp 3 −H bond are formed on the same carbon atom. The stereoselective reaction is general for 2‐, 3‐, and 4‐substituted cyclohexanone tosylhydrazones, as well as for 2‐substituted cyclopentanones. However, no stereoselectivity is observed for acyclic derivatives. DFT computational modeling suggests that the stereoselectivity of the reaction is determined by the approach of the boronic acid to the diazocyclohexane on its most stable chair conformation through an equatorial trajectory.