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B(CF) 共催化剂促进从格拉布催化剂 I 中非常规卤化物的夺取,以提高反应活性并限制分解。

B(CF) Co-Catalyst Promotes Unconventional Halide Abstraction from Grubbs I to Enhance Reactivity and Limit Decomposition.

作者信息

Medley Austin W, Patel Diya, Utne Calvin, Bender Trandon A

机构信息

Department of Chemistry and Biochemistry, Old Dominion University, 4501 Elkhorn Avenue, Norfolk, Virginia 23529, United States.

出版信息

Organometallics. 2024 Oct 23;43(21):2727-2735. doi: 10.1021/acs.organomet.4c00178. eCollection 2024 Nov 11.

Abstract

Ruthenium based Grubbs metathesis has become a commonplace reaction for synthetic chemists. Development of new generations of catalysts evolving from Grubbs I (GI) have led to greater stability, functional group compatibility, and superior reactivities. However, these advancements lead to increased costs. To this end, we report here how the addition of the commercially available tris(pentafluorophenyl)borane Lewis acid, which has become a common place catalyst in its own right, leads to enhanced reactivity of GI. Moreover, the increased reactivity arises via halide abstraction rather than traditional phosphine dissociation, providing ring-opening metathesis polymerization products that are divergent from those synthesized without the Lewis acid cocatalyst.

摘要

基于钌的格拉布催化剂复分解反应已成为合成化学家常用的反应。从第一代格拉布催化剂(GI)发展而来的新一代催化剂具有更高的稳定性、官能团兼容性和更优异的反应活性。然而,这些进步导致成本增加。为此,我们在此报告,添加市售的三(五氟苯基)硼烷路易斯酸(其本身已成为一种常用催化剂)如何提高GI的反应活性。此外,反应活性的提高是通过卤化物提取而非传统的膦解离实现的,从而提供了与无路易斯酸助催化剂合成的产物不同的开环复分解聚合产物。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/22b3/11558663/28d9f79540af/om4c00178_0001.jpg

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