BiBr3 initiated cyclization-addition reactions: effect of π-nucleophile on oxocarbenium ion addition and total syntheses of (+)-(S,S)-(cis-6-methyltetrahydropyran-2-yl)acetic acid and its trans-diastereomer |
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| Authors: | Robert J Hinkle Yajing Lian Nichole D Litvinas Alex T Jenkins Daniel C Burnette |
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| Institution: | Department of Chemistry, The College of William and Mary, PO Box 8795, Williamsburg, VA 23187-8795, USA |
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| Abstract: | For BiBr3 initiated tandem cyclization-additions of very reactive silyl ketene acetal nucleophiles with δ-silyloxy aldehydes to afford 2,6-disubstituted THP products, diastereoselectivities range from 5-6:1 (trans-/cis-). The selectivity for axial attack on the intermediate oxocarbenium ion is inversely proportional to π-nucleophilicity. We have utilized this chemistry to convert a common starting material to both cis- and trans-diastereomers of an acid first isolated from the secretions of Viverra civetta. |
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| Keywords: | Bismuth Bi(III) Oxocarbenium Allylation Etherification Tetrahydropyran |
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