Enantioselective Copper-Catalyzed Borylative Amidation of Allenes
Enantioselective Copper-Catalyzed Borylative Amidation of Allenes
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DOI：
10.1021/jacs.2c10507
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发表时间：
2022-12-06
影响因子：
15
通讯作者：
Scheidt，Karl A.
中科院分区：
文献类型：
--
作者：
Byun，Seunghwan;Farah，Abdikani Omar;Scheidt，Karl A.
公开了一种铜催化合成具有α-立体中心的对映体富集的酰胺的方法。该方法涉及将烯丙基铜物质添加到异氰酸酯中，并允许以高产率和高至优异的对映选择性获得α-取代的手性酰胺。α-乙烯基β-硼基酰胺在合成中的用途突出表现为产物的多样化，以提供高度有用的支架。DFT计算表明，催化剂优先协调的异氰酸酯的氧。手性配体的立体定向苯基与硼基之间的空间排斥作用导致了对映体的控制。
An approach for the copper-catalyzed synthesis of enantioenriched amides bearing an α-stereogenic center is disclosed. This method involves the addition of an allyl copper species to an isocyanate and allows access to α-substituted chiral amides in high yields and high-to-excellent enantioselectivities. The utility of α-vinyl β-boryl amides in synthesis is highlighted by the diversification of products to afford highly useful scaffolds. DFT calculations reveal that the catalyst preferentially coordinates to the oxygen of the isocyanate. Enantiocontrol arises from the steric repulsion between the boryl group and the stereodirecting phenyl of the chiral ligand.