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Rhodium‐Catalyzed Alkene Hydrosilylation via a Hydride Shuttle Process by Diene Ligands: Dramatic Enhancement of Regio‐ and Diastereoselectivity
Author(s) -
Hua Yuanda,
Nguyen Hiep H.,
Trog Gabriela,
Berlin Adam S.,
Jeon Junha
Publication year - 2014
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201402742
Subject(s) - hydrosilylation , chemistry , alkene , diene , ligand (biochemistry) , phosphine , binap , regioselectivity , intramolecular force , hydride , rhodium , allene , medicinal chemistry , catalysis , stereochemistry , combinatorial chemistry , enantioselective synthesis , organic chemistry , metal , biochemistry , natural rubber , receptor
A cooperative ligand‐assisted, Rh‐catalyzed intramolecular alkene hydrosilylation of homoallylic silyl ethers ( 1 ) was developed to provide 1,3‐ trans ‐oxasilacyclopentanes ( trans ‐ 2 ) in a highly regio‐ and diastereoselective manner. The modification of metal‐ligand architecture employing an inner‐sphere functional diene ligand (1,3‐cyclohexadiene) and a supporting phosphine ligand (BINAP) was identified as responsible for dramatic enhancement of selectivities. Mechanistic details of a diene ligand‐mediated hydride shuttle process are presented as the potential mechanistic driving force behind the high level of the selectivities.