通过TEMPO+BF4介导的脱水Nazarov环化对映选择性合成Fortalpinoid Q

IF 15.6 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Journal of the American Chemical Society Pub Date : 2025-03-10 DOI:10.1021/jacs.5c00319

Hai-Kang Mao, Qian Wang, Jing Xu

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引用次数: 0

摘要

头孢类二萜家族代表了一类迷人的天然产物，从结构和生物学的角度来看都引起了我们的浓厚兴趣。在此，我们希望报告一种 15 步、对映选择性全合成头孢噻肟二萜类化合物福尔他匹胺 Q 的方法。我们的方法主要包括：(1) 通过雅各布森催化的对映体选择性克莱森重排，只需一步就能形成两个副立体中心，包括一个全碳季中心；(2) 温和的氧铵盐（TEMPO+BF4-）促进的脱水纳扎罗夫环化反应，通过未官能化的叔二乙烯基甲醇（TDC）底物迅速形成关键的环戊二烯分子；以及 (3) 便捷的醛醇-内酯化级联反应，最终解决了合成中的最后一个障碍。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

Enantioselective Total Synthesis of Fortalpinoid Q via a TEMPO+BF4–-Mediated Dehydrative Nazarov Cyclization

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Enantioselective Total Synthesis of Fortalpinoid Q via a TEMPO+BF4–-Mediated Dehydrative Nazarov Cyclization

The family of Cephalotaxus diterpenoids represents a captivating class of natural products that are of significant interest from both structural and biological perspectives within our community. Here we wish to report a 15-step, enantioselective total synthesis of the Cephalotaxus diterpenoid fortalpinoid Q. Our approach highlights (1) a Jacobsen’s catalytic enantioselective Claisen rearrangement that enabled the single-step formation of two vicinal stereogenic centers, including an all-carbon quaternary center; (2) a mild, oxoammonium salt (TEMPO⁺BF₄^–)-promoted dehydrative Nazarov cyclization that swiftly forged the crucial cyclopentadiene moiety via an unfunctionalized tertiary divinyl carbinol (TDC) substrate; and (3) a facile aldol-lactonization cascade that ultimately resolved the last obstacle in the synthesis.

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来源期刊

Journal of the American Chemical Society 化学-化学综合

CiteScore

24.40

自引率

6.00%

发文量

2398

审稿时长

1.6 months

期刊介绍： The flagship journal of the American Chemical Society, known as the Journal of the American Chemical Society (JACS), has been a prestigious publication since its establishment in 1879. It holds a preeminent position in the field of chemistry and related interdisciplinary sciences. JACS is committed to disseminating cutting-edge research papers, covering a wide range of topics, and encompasses approximately 19,000 pages of Articles, Communications, and Perspectives annually. With a weekly publication frequency, JACS plays a vital role in advancing the field of chemistry by providing essential research.