Enantioselective Heck/Tsuji−Trost reaction of flexible vinylic halides with 1,3-dienes

IF 15.7 1区综合性期刊 Q1 MULTIDISCIPLINARY SCIENCES Nature Communications Pub Date : 2025-01-22 DOI:10.1038/s41467-025-56142-z

Li-Zhi Zhang, Pei-Chao Zhang, Qian Wang, Min Zhou, Junliang Zhang

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Abstract

The enantioselective domino Heck/cross-coupling has emerged as a powerful tool in modern chemical synthesis for decades. Despite significant progress in relative rigid skeleton substrates, the implementation of asymmetric Heck/cross-coupling cascades of highly flexible haloalkene substrates remains a challenging and and long-standing goal. Here we report an efficient asymmetric domino Heck/Tsuji−Trost reaction of highly flexible vinylic halides with 1,3-dienes enabled by palladium catalysis. Specifically, the Heck insertion as stereodetermining step to form ƞ³ allyl palladium complex and in situ trapping with nucleophiles enable efficient Heck/etherification in a formal (4 + 2) cycloaddition manner. Engineering the Sadphos bearing androgynous non-C₂-symmetric chiral sulfinamide phosphine ligands are vital component in achieving excellent catalytic reactivity and enantioselectivity. This strategy offers a general, modular and divergent platform for rapidly upgrading feedstock flexible vinylic halides and dienes to various value-added molecules and is expected to inspire the development of other challenging enantioselective domino Heck/cross-couplings.

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柔性乙烯卤化物与1,3-二烯的对映选择性Heck/Tsuji−Trost反应

几十年来，对映选择性多米诺骨牌Heck/交叉偶联已成为现代化学合成的有力工具。尽管在相对刚性骨架衬底方面取得了重大进展，但实现高度柔性卤代烃衬底的不对称Heck/交叉耦合级联仍然是一个具有挑战性和长期的目标。在这里，我们报道了一个高效的不对称多米诺Heck/Tsuji−Trost反应，高柔性乙烯卤化物与1,3-二烯在钯催化下实现。具体来说，Heck插入作为立体决定步骤形成ƞ3烯丙基钯配合物和亲核试剂的原位捕获使Heck/醚化以正式的（4 + 2）环加成方式有效。设计具有雌雄同体非c2对称手性亚砜酰胺膦配体的Sadphos是获得优异催化反应活性和对映选择性的重要组成部分。该策略为快速将原料柔性乙烯卤化物和二烯升级为各种增值分子提供了通用、模块化和多样化的平台，并有望激发其他具有挑战性的对映选择性多米诺骨牌Heck/交叉偶联的发展。

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来源期刊

Nature Communications Biological Science Disciplines-

CiteScore

24.90

自引率

2.40%

发文量

6928

审稿时长

3.7 months

期刊介绍： Nature Communications, an open-access journal, publishes high-quality research spanning all areas of the natural sciences. Papers featured in the journal showcase significant advances relevant to specialists in each respective field. With a 2-year impact factor of 16.6 (2022) and a median time of 8 days from submission to the first editorial decision, Nature Communications is committed to rapid dissemination of research findings. As a multidisciplinary journal, it welcomes contributions from biological, health, physical, chemical, Earth, social, mathematical, applied, and engineering sciences, aiming to highlight important breakthroughs within each domain.