A Concise Total Synthesis of Saliniketal B

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• 作者：Jun Liu ; Jef K. De Brabander
• 刊名：Journal of the American Chemical Society
• 出版年：2009
• 出版时间：September 9, 2009
• 年：2009
• 卷：131
• 期：35
• 页码：12562-12563
• 全文大小：185K
• 年卷期：v.131,no.35(September 9, 2009)
• ISSN：1520-5126

文摘

We report a concise, enantioselective, and highly efficient synthesis of the marine actinomycete-derived natural product saliniketal B. Our approach was motivated with an eye toward future structure−function studies of this inhibitor of phorbol ester-mediated ornithine decarboxylase induction via an unknown mechanism. Our strategy highlights the utility of Pt(II)-mediated cycloisomerization of alkynediols developed in our laboratory to construct the dioxabicyclo[3.2.1]octane ring system, a highly selective aldol fragment coupling whose stereochemical outcome is influenced by a γ-stereogenic methyl group, and an interesting one-pot desilylation/dihydropyranone fragmentation/amidation sequence. As such, saliniketal B was obtained in 11 steps and 23% overall yield from commercially available starting material via a convergent coupling of two equally complex fragments assembled in seven and eight steps (39 and 45%), respectively.