配体激活的化学和区域选择性Ir(I)催化的烯类分子间碳酸化反应:获得具有全碳四元中心的支链产物

Alejandro Rey, Dr. Andrés Arribas, Prof. Dr. José L. Mascareñas, Dr. Fernando López
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引用次数: 0

摘要

以全氟双膦配体dFppe为特征的铱配合物可以催化烯的分子间羰化反应,并精确控制选择性,生成高价值的支链产物,而不是更常见的线性衍生物。使用n取代的3-羧基酰胺吡咯作为C─H给体,反应只产生C-4取代产物,而呋喃类似物产生C-2取代衍生物。β-未取代丙烯酰胺也可用作C─H源得到手性跳过二烯。单取代和1,1-二取代烯的加成同样有效,能够有效地形成具有叔碳和全碳季位立体中心的产物。此外,对手性二亚磷酸盐配体的初步分析证实了对映选择性变异的可行性。计算(DFT)研究提供了相关的见解,这种显著的配体驱动的分支选择性。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Ligand-Enabled Chemo- and Regioselective Ir(I)-Catalyzed Intermolecular Hydrocarbonation of Allenes: Access to Branched Products with All-Carbon Quaternary Centers

Ligand-Enabled Chemo- and Regioselective Ir(I)-Catalyzed Intermolecular Hydrocarbonation of Allenes: Access to Branched Products with All-Carbon Quaternary Centers

An iridium complex featuring the perfluorinated bisphosphine ligand dFppe can catalyze intermolecular hydrocarbonation reactions of allenes with precise control over the selectivity to yield highly valuable branched products instead of the more common linear derivatives. Using N-substituted 3-carboxamide pyrroles as C─H donors, the reaction gives exclusively C-4 substituted products, while furan analogues yield C-2 substituted derivatives. β-Unsubstituted acrylamides can also be used as C─H sources to give chiral skipped dienes. The additions are equally efficient using monosubstituted and 1,1-disubstituted allenes, enabling the efficient formation of products bearing tertiary and all-carbon quaternary stereocenters. Moreover, a preliminary analysis with chiral bisphosphinite ligands confirms the feasibility of an enantioselective variant. Computational (DFT) studies provide relevant insights into this remarkable ligand-driven branched selectivity.

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来源期刊
Angewandte Chemie
Angewandte Chemie 化学科学, 有机化学, 有机合成
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