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Stereodivergent Alkyne Reduction by using Water as the Hydrogen Source
Author(s) -
Rao Santhosh,
Prabhu Kandikere Ramaiah
Publication year - 2018
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.201803147
Subject(s) - alkyne , chemistry , reagent , phosphine , stereoselectivity , yield (engineering) , ligand (biochemistry) , combinatorial chemistry , catalysis , homogeneous , organic chemistry , materials science , biochemistry , receptor , metallurgy , physics , thermodynamics
A homogeneous Pd‐catalyzed stereodivergent reduction of alkynes to Z and E alkenes by using H 2 O as the H 2 source is presented. Mediated by a diboron reagent, the transfer hydrogenation has been accomplished to yield the desired geometrical isomer by rational ligand selection. The switchable stereoselectivity achieved using simple phosphine ligands is generally excellent. D 2 O has also been used as a D 2 source for synthesizing the corresponding deuterated olefins. Supported by a gram‐scale synthesis, the reaction can easily be scaled up making it an efficient way to prepare alkenes commercially as well. Mechanistic studies suggest formation of H−PdL 2 −OAc as the crucial step leading to the presence of two pathways involving H−Pd−B(OR) 2 and molecular H 2 as active intermediates.