Publication: Asymmetric synthesis of gem-difluoromethylenated dihydroxypyrrolizidines and indolizidines
Issued Date
2012-10-05
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ISSN
15206904
00223263
00223263
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2-s2.0-84867381413
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Mahidol University
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SCOPUS
Bibliographic Citation
Journal of Organic Chemistry. Vol.77, No.19 (2012), 8465-8479
Suggested Citation
Watcharaporn Thaharn, Teerawut Bootwicha, Darunee Soorukram, Chutima Kuhakarn, Samran Prabpai, Palangpon Kongsaeree, Patoomratana Tuchinda, Vichai Reutrakul, Manat Pohmakotr Asymmetric synthesis of gem-difluoromethylenated dihydroxypyrrolizidines and indolizidines. Journal of Organic Chemistry. Vol.77, No.19 (2012), 8465-8479. doi:10.1021/jo301327s Retrieved from: https://repository.li.mahidol.ac.th/handle/20.500.14594/13940
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Title
Asymmetric synthesis of gem-difluoromethylenated dihydroxypyrrolizidines and indolizidines
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Abstract
An asymmetric synthesis of gem-difluoromethylenated dihydroxypyrrolizidines and indolizidines is described. The fluoride-catalyzed nucleophilic addition of PhSCF 2 SiMe 3 (1) to chiral imides was achieved in satisfactory yields to provide mixtures of syn- and anti-isomers 6-9 with moderate to good diastereoselectivities. Reductive cleavage of the phenylsulfanyl group followed by intramolecular radical cyclization of the syn-isomers 6-9 occurred under refluxing conditions to afford the corresponding gem-difluoromethylenated 1-azabicyclic compounds 10-13 in moderate yields as a separable mixture of cis- and trans-isomers. The cis-isomers of compounds 10 and 12 and trans-13 were readily transformed to gem-difluoromethylenated dihydroxypyrrolizidines 20 and 27 and indolizidine 28, respectively, by reductive cleavage of the hydroxyl group and organometallic addition followed by hydrogenolysis. © 2012 American Chemical Society.