Publication: Asymmetric synthesis of gem -difluoromethylenated linear triquinanes via cascade gem -difluoroalkyl radical cyclization
Issued Date
2015-01-16
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ISSN
15206904
00223263
00223263
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2-s2.0-84921296200
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Mahidol University
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SCOPUS
Bibliographic Citation
Journal of Organic Chemistry. Vol.80, No.2 (2015), 816-827
Suggested Citation
Watcharaporn Thaharn, Darunee Soorukram, Chutima Kuhakarn, Patoomratana Tuchinda, Chaveng Pakawatchai, Saowanit Saithong, Vichai Reutrakul, Manat Pohmakotr Asymmetric synthesis of gem -difluoromethylenated linear triquinanes via cascade gem -difluoroalkyl radical cyclization. Journal of Organic Chemistry. Vol.80, No.2 (2015), 816-827. doi:10.1021/jo5022579 Retrieved from: https://repository.li.mahidol.ac.th/handle/20.500.14594/35760
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Title
Asymmetric synthesis of gem -difluoromethylenated linear triquinanes via cascade gem -difluoroalkyl radical cyclization
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Abstract
© 2014 American Chemical Society. An asymmetric synthesis of gem-difluoromethylenated linear triquinanes is described exploiting the synthetic utilities of PhSCF<inf>2</inf>TMS (5) as a "<sup>•</sup>CF<inf>2</inf><sup>-</sup> building block. The strategy involves fluoride-catalyzed nucleophilic addition of PhSCF<inf>2</inf>TMS (5) to chiral ketocyclopentenes 6 to provide silylated adducts 9 or alcohol derivatives 10 and 11. Subsequent cascade radical cyclization of the gem-difluoroalkyl radical generated from silylated adducts 9 or alcohols 10 and 11 afforded gem-difluoromethylenated linear triquinanes 16 as an approximate 1:1 mixture of two diastereomers (16A and 16B). Alternatively, a convenient asymmetric synthesis of gem-difluoromethylenated linear triquinanes 16A can be accomplished by oxidation of 16a (R = H) to provide ketotriquinane 17 followed by a highly stereoselective nucleophilic addition to 17 employing DIBAL, NaBH<inf>4</inf>, and various Grignard reagents.