☆ 4.8 Article

Constructing Quaternary Stereogenic Centers Using Tertiary Organocuprates and Tertiary Radicals. Total Synthesis of trans-Clerodane Natural Products

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2015)

期刊

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY

卷 137, 期 2, 页码 660-663

出版社

AMER CHEMICAL SOC

DOI: 10.1021/ja512527s

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Chemistry, Multidisciplinary

资金

National Science Foundation [CHE1265964]
Swiss National Science Foundation
German Academic Exchange Service (DAAD)
Direct For Mathematical & Physical Scien [1265964] Funding Source: National Science Foundation
Division Of Chemistry [1265964] Funding Source: National Science Foundation

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摘要

A new concise construction of trans-clerodane diterpenoids is reported in which oxacyclic and trans-hydronaphthalene fragments are coupled, and the critical C9-quaternary carbon stereocenter formed stereoselectively, by 1,6-addition of a tertiary cuprate or a tertiary carbon radical to beta-vinylbutenolide. This strategy is specifically illustrated by total syntheses of (-)-solidagolactone (4), (-)-16-hydroxycleroda-3,13-dien-15,16-olide (5, PL3), and (-)-annonene (6).

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