TY - JOUR
T1 - Metal-free transfer hydrogenation of olefins via dehydrocoupling catalysis
AU - Pérez, Manuel
AU - Caputo, Christopher B.
AU - Dobrovetsky, Roman
AU - Stephan, Douglas W.
PY - 2014
Y1 - 2014
N2 - A major advance in main-group chemistry in recent years has been the emergence of the reactivity of main-group species that mimics that of transition metal complexes. In this report, the Lewis acidic phosphonium salt [(C 6F5)3PF][B(C6F5) 4] 1 is shown to catalyze the dehydrocoupling of silanes with amines, thiols, phenols, and carboxylic acids to form the Si-E bond (E = N, S, O) with the liberation of H2 (21 examples). This catalysis, when performed in the presence of a series of olefins, yields the concurrent formation of the products of dehydrocoupling and transfer hydrogenation of the olefin (30 examples). This reactivity provides a strategy for metal-free catalysis of olefin hydrogenations. The mechanisms for both catalytic reactions are proposed and supported by experiment and density functional theory calculations.
AB - A major advance in main-group chemistry in recent years has been the emergence of the reactivity of main-group species that mimics that of transition metal complexes. In this report, the Lewis acidic phosphonium salt [(C 6F5)3PF][B(C6F5) 4] 1 is shown to catalyze the dehydrocoupling of silanes with amines, thiols, phenols, and carboxylic acids to form the Si-E bond (E = N, S, O) with the liberation of H2 (21 examples). This catalysis, when performed in the presence of a series of olefins, yields the concurrent formation of the products of dehydrocoupling and transfer hydrogenation of the olefin (30 examples). This reactivity provides a strategy for metal-free catalysis of olefin hydrogenations. The mechanisms for both catalytic reactions are proposed and supported by experiment and density functional theory calculations.
KW - Fluorophosphonium
UR - http://www.scopus.com/inward/record.url?scp=84904985328&partnerID=8YFLogxK
U2 - 10.1073/pnas.1407484111
DO - 10.1073/pnas.1407484111
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AN - SCOPUS:84904985328
SN - 0027-8424
VL - 111
SP - 10917
EP - 10921
JO - Proceedings of the National Academy of Sciences of the United States of America
JF - Proceedings of the National Academy of Sciences of the United States of America
IS - 30
ER -