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交让木生物碱：（-）-去甲乌药碱的全合成。

The daphniphyllum alkaloids: total synthesis of (-)-calyciphylline N.

作者信息

Shvartsbart Artem, Smith Amos B

机构信息

Department of Chemistry, Laboratory for Research on the Structure of Matter, and Monell Chemical Senses Center, University of Pennsylvania, Philadelphia, Pennsylvania 19104, United States.

出版信息

J Am Chem Soc. 2015 Mar 18;137(10):3510-9. doi: 10.1021/ja503899t. Epub 2015 Mar 10.

DOI:10.1021/ja503899t
PMID:25756504
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC4394112/
Abstract

Presented here is a full account on the development of a strategy culminating in the first total synthesis of the architecturally complex daphniphyllum alkaloid, (-)-calyciphylline N. Highlights of the approach include a highly diastereoselective, intramolecular Diels-Alder reaction of a silicon-tethered acrylate; an efficient Stille carbonylation of a sterically encumbered vinyl triflate; a one-pot Nazarov cyclization/proto-desilylation sequence; and the chemoselective hydrogenation of a fully substituted diene ester.

摘要

本文全面阐述了一种策略的发展过程，该策略最终实现了对结构复杂的虎皮楠生物碱（-）-calyciphylline N的首次全合成。该方法的亮点包括硅连接丙烯酸酯的高度非对映选择性分子内狄尔斯-阿尔德反应；空间位阻较大的乙烯基三氟甲磺酸酯的高效施蒂勒羰基化反应；一锅法的纳扎罗夫环化/原脱硅反应序列；以及全取代二烯酯的化学选择性氢化反应。

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