Novel rearrangement of chloromethylvinylsilanes into allylsilanes. Stereoselective synthesis of metallated allylsilanes from 1-alkynes |
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| Institution: | 1. Bristol-Myers Squibb, Research and Development, 5 Research Parkway, Wallingford, CT 06492, USA;2. Bristol-Myers Squibb, Research and Development, PO Box 4000, Princeton, NJ 08540, USA;1. Department of Medicinal Chemistry, Key Laboratory of Chemical Biology (Ministry of Education), School of Pharmaceutical Sciences, Shandong University, 44 West Culture Road, Jinan 250012, China;2. The Affiliated Hospital of Qingdao University, Qingdao 266003, China;3. School of Pharmacy and Medical Sciences, Sansom Institute for Health Research, University of South Australia, Adelaide, SA 5000, Australia;1. Department of Chemistry, National University of Singapore, 3 Science Drive 3, 117543, Singapore;2. Sustainable Energy Laboratory, China University of Geosciences Wuhan, 388 Lumo RD, Wuhan 430074, China |
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| Abstract: | Regio and stereoselective hydralumination of 1-(chloromethyldimethylsilyl)-1-alkyne with diisobutylaluminium hydride (DIBAH) affords (Z)-1-(chloromethyldimethylsilyl)-1-(diisobutylalumino)-1-alkene. Treatment of the aluminium-substituted vinylsilane with 3 equivalents of methyllithium affords (E)-1-(trimethylsilyl)-2-lithio-2-alkene as a sole product. Reaction of aluminium-substituted vinylsilane with trimethylaluminium in refluxing heptane produces a mixture of (E)-1-trimethyl-silyl-2-alumino-2-alkene and 2-trimethylsilyl-1-alkene. Reaction of 1-(chloromethyldimethylsilyl)-1-alkyne with triisobutylaluminium gives 2-(isobutyldimethylsilyl)-1-alkene exclusively. Reactions of the lithiated allylsilane with several electrophiles give the corresponding carbometallated products, allylsilanes bearing alkyl, allyl, vinyl, or alkoxycarbonyl groups. Protodesilylation of 3-(trimethylsilylmethyl)-1,3-decadiene gives 3-methylene-1-decene selectively. Reaction of trialkylaluminium with trimethylsilylethyne gives bistrimethylsilylated diene by successive addition of silylethyne to the aluminium reagent; in contrast, chloromethyldimethylsilylethyne gives the mono-adduct regio and stereoselectively. |
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