Rhodium‐Catalyzed Alkene Hydrosilylation via a Hydride Shuttle Process by Diene Ligands: Dramatic Enhancement of Regio‐ and Diastereoselectivity1. Issue 27 (21st August 2014)

• Record Type: Journal Article
• Authors: Hua, Yuanda; Nguyen, Hiep H.; Trog, Gabriela; Berlin, Adam S.; Jeon, Junha
• Is Part Of: European journal of organic chemistry. Issue 27(2014)
• Page Start: 5890
• Page End: 5895
• Publication Date: 2014-08-21
• Subjects: Homogeneous catalysis -- Rhodium -- Hydrosilylation -- Hydride shuttle -- Diene ligands -- Cyclization; Chemistry, Organic -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1002/ejoc.201402742
• Languages: English
• ISSNs: 1434-193X

Abstract

Abstract: 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. Abstract : A cooperative functional diene ligand and a supporting phosphine ligand mediated, Rh‐catalyzed intramolecular alkene hydrosilylation of homoallylic silyl ethers was developed to provide 1, 3‐ trans ‐oxasilacyclopentanes in a highly regio‐ and diastereoselective manner. A diene ligand mediated hydride shuttle process is proposed as the mechanistic driving force behind the high level of selectivities.