Highly Enantioselective Hydroformylation of Aryl Alkenes with Diazaphospholane Ligands
Highly Enantioselective Hydroformylation of Aryl Alkenes with Diazaphospholane Ligands
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DOI：
10.1021/ol801723a
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发表时间：
2008-10-16
期刊：
影响因子：
5.2
通讯作者：
Landis, Clark R.
中科院分区：
文献类型：
--
作者：
Watkins, Avery L.;Hashiguchi, Brian G.;Landis, Clark R.
不对称，铑催化的末端和内部芳烯烃与二氮磷烷配体的氢甲酰化。在部分优化的反应条件下，对大多数底物获得了高的对映选择性（> - 90% ee）和区域选择性（高达65:1 α: β）。对于末端烯烃，对映体选择性和区域选择性都与一氧化碳分压成正比，但与氢压力无关。对取代苯乙烯衍生物的氢甲酰化对带有吸电子取代基的底物具有最高的区域选择性。哈米特分析得出区域选择性呈正线性相关。
Asymmetric, rhodium-catalyzed hydroformylation of terminal and internal aryl alkenes with diazaphospholane ligands is reported. Under partially optimized reaction conditions, high enantioselectivity (>90% ee) and regioselectivities (up to 65:1 alpha:beta) are obtained for most substrates. For terminal alkenes, both enantioselectivity and regioselectivity are proportional to the carbon monoxide partial pressure, but independent of hydrogen pressure. Hydroformylation of para-substituted styrene derivatives gives the highest regioselectivity for substrates bearing electron-withdrawing substituents. A Hammett analysis produces a positive linear correlation for regioselectivity.