用于区域选择性铑催化苯乙烯氢甲酰化反应生成直链醛的SUPRAPhos配体。

SUPRAPhos ligands for the regioselective rhodium catalyzed hydroformylation of styrene forming the linear aldehyde.

作者信息

Goudriaan P Elsbeth, Kuil Mark, Jiang Xiao-Bin, van Leeuwen Piet W N M, Reek Joost N H

机构信息

Homogeneous and Supramolecular Chemistry, Van't Hoff Institute for Molecular Sciences, Nieuwe Achtergracht 166, 1018 WV, Amsterdam, The Netherlands.

出版信息

Dalton Trans. 2009 Mar 14(10):1801-5. doi: 10.1039/b818665k. Epub 2009 Jan 23.

DOI:10.1039/b818665k

PMID:19240914

Abstract

We report SUPRAphos-based rhodium catalysts that are unusually regioselective in the hydroformylation of styrene at low temperatures (40 degrees C) producing mainly the linear aldehyde (72%). This ligand-specific phenomenon is observed for two rhodium catalysts with heterobidentate phosphine-phosphoramidite ligands. We propose that the high selectivity for the linear product is caused by enhanced beta-hydride elimination, due to specific substrate-ligand interactions, most likely pi-pi interactions.

摘要

我们报道了基于SUPRAphos的铑催化剂，该催化剂在低温（40摄氏度）下对苯乙烯的氢甲酰化反应具有异常的区域选择性，主要生成线性醛（72%）。对于两种带有异双齿膦-磷酰胺配体的铑催化剂，都观察到了这种配体特异性现象。我们认为，线性产物的高选择性是由于特定的底物-配体相互作用（很可能是π-π相互作用）增强了β-氢消除所致。