Journal
ACS CATALYSIS
Volume 9, Issue 2, Pages 1612-1618Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acscatal.8b04481
Keywords
cobalt; conjugated dienes; allylsilane; polyorganosiloxane; hydrosilylation; asymmetric catalysis
Categories
Funding
- Ministry of Science and Technology of China [2016YFA0202900, 2015CB856600]
- NSFC [21825109, 21732006, 21432011, 21602236]
- Chinese Academy of Sciences [XDB20000000, QYZDB-SSW-SLH016]
- Science and Technology Commission of Shanghai Municipality [17JC1401200]
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The asymmetric 1,2-Markovnikov hydrosilylation of conjugated dienes with primary silanes catalyzed by a quinoline-oxazoline cobalt complex has been described. This protocol provides an efficient approach to chiral allyl dihydrosilanes with high regioselectivity and enantioselectivity (up to 96% ee). The catalyst system is effective for a wide array of conjugated dienes, including mono- and 1,2-disubstituted dienes with aryl and/or alkyl substituents. Further, the products are applied to the synthesis of polyorganosiloxanes (organo-silicone copolymers) containing side chains of enantioenriched allylic functionalities using a pyridine-oxazoline cobalt-catalyzed step-growth polymerization with terephthalaldehyde. The result of a deuterium-labeling experiment involving the reaction of PhSiD3 and 1,3-pentadiene suggests that the hydrosilylation most likely proceeds through a modified Chalk-Harrod mechanism involving the 1,2-insertion of the terminal double bond of the diene into the Co-Si bond.
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