Tandem asymmetric dearomatized functionalization reaction of phenols with Evans-ynamides enabled by divergent electrophiles

IF 10.4 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Science China Chemistry Pub Date : 2024-09-13 DOI:10.1007/s11426-024-2211-y

Ying-Qi Zhang, Gan-Lu Qian, Yun Liu, Jia-Hui Li, Xin Hong, Zhou Xu, Bo Zhou, Long-Wu Ye

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引用次数: 0

Abstract

Herein, we disclose a highly regio-/chemoselective tandem asymmetric dearomatized halofunctionalization reaction of phenol-tethered ynamides with diverse electrophilic halogenation sources in a catalyst-free manner for the practical and rapid assembly of a series of halogenated spirocyclic enones. Besides, the related dearomatized selenation and protonation are also achieved, affording the corresponding selenated and protonated spirocycles in high efficiency. Moreover, the enantioselectivities of these products can be perfectly induced by Evans auxiliaries (99% ees). Significantly, this protocol not only represents the first tandem asymmetric halofunctionalization reaction of phenol derivatives, but also constitutes the first asymmetric halogenation/selenation of ynamides. Theoretical calculations indicate a remote induction model of Evans chiral auxiliary-attached keteniminium.

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利用发散亲电体实现苯酚与伊文炔酰胺的串联不对称脱芳烃官能化反应

在此，我们以无催化剂的方式，揭示了苯酚系炔酰胺与多种亲电卤化源的高区域/化学选择性串联不对称脱芳烃卤化反应，从而实用、快速地组装出一系列卤代螺环烯酮。此外，还实现了相关的脱芳烃硒化和质子化，从而高效地得到了相应的硒化和质子化螺环。此外，这些产物的对映选择性可以通过伊文思助剂完美地诱导出来（99% 的对映选择性）。值得注意的是，该方案不仅代表了苯酚衍生物的首次串联不对称卤化反应，而且也是酰肼的首次不对称卤化/硒化反应。理论计算表明，埃文斯手性助剂连接的酮亚胺是一个遥控诱导模型。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Science China Chemistry CHEMISTRY, MULTIDISCIPLINARY-

CiteScore

14.40

自引率

7.30%

发文量

3787

审稿时长

2.2 months

期刊介绍： Science China Chemistry, co-sponsored by the Chinese Academy of Sciences and the National Natural Science Foundation of China and published by Science China Press, publishes high-quality original research in both basic and applied chemistry. Indexed by Science Citation Index, it is a premier academic journal in the field. Categories of articles include: Highlights. Brief summaries and scholarly comments on recent research achievements in any field of chemistry. Perspectives. Concise reports on thelatest chemistry trends of interest to scientists worldwide, including discussions of research breakthroughs and interpretations of important science and funding policies. Reviews. In-depth summaries of representative results and achievements of the past 5–10 years in selected topics based on or closely related to the research expertise of the authors, providing a thorough assessment of the significance, current status, and future research directions of the field.