烯烃与原位生成的 N-Boc-Formaldimine 的催化不对称环加成。

IF 14.4 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Journal of the American Chemical Society Pub Date : 2024-11-18 DOI:10.1021/jacs.4c13538

Marian Guillén, Markus Leutzsch, Benjamin List

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引用次数: 0

摘要

手性 1,3-氨基醇是天然产品和活性药物成分中无处不在的结构基团。我们介绍了在强约束 Bro̷nsted 酸催化下，烯烃与原位生成的 N-Boc-formaldimine 发生的高对映选择性、反电子需求的异 Diels-Alder 反应。这种转化可以直接从苯乙烯和 1,1- 二亚硝基烯烃中获得有价值的 1,3- 氨基醇。同位素标记研究和动力学分析揭示了一种不寻常的机理，其中涉及一个草铵中间体和一个大于 1 的催化剂阶数。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

Catalytic Asymmetric Cycloaddition of Olefins with In Situ Generated N-Boc-Formaldimine.

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Catalytic Asymmetric Cycloaddition of Olefins with In Situ Generated N-Boc-Formaldimine.

Chiral 1,3-amino alcohols are ubiquitous structural motifs in natural products and active pharmaceutical ingredients. We present a highly enantioselective, inverse-electron-demand hetero-Diels-Alder reaction of olefins with in situ generated N-Boc-formaldimine catalyzed by strong and confined Bro̷nsted acids. This transformation provides direct access to valuable 1,3-amino alcohols from styrenes and 1,1-disubtituted alkenes. Isotope labeling studies and kinetic analysis reveal an unusual mechanism involving an oxazinium intermediate and a catalyst order greater than one.

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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.