Contra-thermodynamic Olefin Isomerization by Chain-Walking Hydrofunctionalization and Formal Retro-hydrofunctionalization

Journal Article · Mon Aug 19 00:00:00 EDT 2019 · Organic Letters

DOI:https://doi.org/10.1021/acs.orglett.9b02695· OSTI ID:1633241

Hanna, Steven ^[1]; Butcher, Trevor W. ^[1]; Hartwig, John F. ^[1]

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1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)

Here, we report a contra-thermodynamic isomerization of internal olefins to terminal olefins driven by redox reactions and formation of Si–F bonds. This process involves chain-walking hydrosilylation of internal olefins and subsequent formal retro-hydrosilylation. The process rests upon the high activities of platinum hydrosilylation catalysts for isomerization of metal alkyl intermediates and a new, metal-free process for the conversion of alkylsilanes to alkenes. By this approach, 1,2-disubstituted and trisubstituted olefins are converted to terminal olefins.

• Research Organization: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
• Sponsoring Organization: Chevron; National Science Foundation (NSF); USDOE Office of Science (SC)
• Grant/Contract Number: AC02-05CH11231
• OSTI ID: 1633241
• Journal Information: Organic Letters, Journal Name: Organic Letters Journal Issue: 17 Vol. 21; ISSN 1523-7060; ISSN 1523-7052
• Publisher: American Chemical Society
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Alkyls
Anions
Hydrocarbons
Hydrosilylation
Isomerization