Intermolecular Carbonyl-olefin Metathesis with Vinyl Ethers Catalyzed by Homogeneous and Solid Acids in Flow
Intermolecular Carbonyl-olefin Metathesis with Vinyl Ethers Catalyzed by Homogeneous and Solid Acids in Flow
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DOI：
10.1002/anie.201909597
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发表时间：
2019-10-04
影响因子：
16.6
通讯作者：
Leyva-Perez, Antonio
中科院分区：
文献类型：
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作者：
Angel Rivero-Crespo, Miguel;Tejeda-Serrano, Maria;Leyva-Perez, Antonio
羰基-烯烃的反应在过去的七年中有了很大的进展，有了新的催化剂和反应方案。然而，这些方法大多涉及可溶催化剂，用于批量分子内反应。本研究表明，可回收、廉价、易处理、无毒且广泛使用的简单固体酸，如铝硅酸盐蒙脱土，可以催化芳香酮和醛与乙烯醚在分子间进行羰基-烯烃的转化反应，得到具有完全反式立体选择性的多克级烯烃，收率高。实验和计算数据支持基于碳正离子诱导的Grob碎裂机制。这些结果为固体催化剂上羰基-烯烃连续反应的工业化实现开辟了道路，这仍然是母烃-烯烃交叉反应的起源和主要应用。
The carbonyl-olefin metathesis reaction has experienced significant advances in the last seven years with new catalysts and reaction protocols. However, most of these procedures involve soluble catalysts for intramolecular reactions in batch. Herein, we show that recoverable, inexpensive, easy to handle, non-toxic, and widely available simple solid acids, such as the aluminosilicate montmorillonite, can catalyze the intermolecular carbonyl-olefin metathesis of aromatic ketones and aldehydes with vinyl ethers in-flow, to give alkenes with complete trans stereoselectivity on multi-gram scale and high yields. Experimental and computational data support a mechanism based on a carbocation-induced Grob fragmentation. These results open the way for the industrial implementation of carbonyl-olefin metathesis over solid catalysts in continuous mode, which is still the origin and main application of the parent alkene-alkene cross-metathesis.