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Cobalt-catalyzed regioselective stereoconvergent Markovnikov 1,2-hydrosilylation of conjugated dienes

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Abstract

We report the first stereoconvergent Markovnikov 1,2-hydrosilylation of conjugated dienes using catalysts generated from bench-stable Co(acac)2 and phosphine ligands. A wide range of E/Z-dienes underwent this Markovnikov 1,2-hydrosilylation in a stereoconvergent manner, affording (E)-allylsilanes in high isolated yields with high stereoselectivities (E/Z = >99 : 1) and high regioselectivities (b/l up to > 99 : 1). Mechanistic studies revealed that this stereoconvergence stems from a σ–π–σ isomerization of an allylcobalt species generated by the 1,4-hydrometalation of Z-dienes. In addition, a cobalt catalyst that can only catalyze the hydrosilylation of the E-isomer of an (E/Z)-diene was identified, which allows the separation of the (Z)-isomer from an isomeric mixture of (E/Z)-dienes. Furthermore, asymmetric hydrosilylation of (E)-1-aryl-1,3-dienes was studied with Co(acac)2/(R)-difluorphos and good enantioselectivities (er up to 90 : 10) were obtained.

Graphical abstract: Cobalt-catalyzed regioselective stereoconvergent Markovnikov 1,2-hydrosilylation of conjugated dienes

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Publication details

The article was received on 12 Sep 2017, accepted on 26 Nov 2017 and first published on 27 Nov 2017


Article type: Edge Article
DOI: 10.1039/C7SC04002D
Citation: Chem. Sci., 2018, Advance Article
  • Open access: Creative Commons BY license
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    Cobalt-catalyzed regioselective stereoconvergent Markovnikov 1,2-hydrosilylation of conjugated dienes

    H. L. Sang, S. Yu and S. Ge, Chem. Sci., 2018, Advance Article , DOI: 10.1039/C7SC04002D

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