Rapid Asymmetric Transfer Hydroformylation (ATHF) of Disubstituted Alkenes Using Paraformaldehyde as a Syngas Surrogate.
Rapid Asymmetric Transfer Hydroformylation (ATHF) of Disubstituted Alkenes Using Paraformaldehyde as a Syngas Surrogate.
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DOI：
10.1002/chem.201502049
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发表时间：
2015-07-20
期刊：
影响因子：
--
通讯作者：
Clarke ML
中科院分区：
文献类型：
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作者：
Fuentes JA;Pittaway R;Clarke ML
作为传统不对称氢甲酰化（AHF）的替代品，本文报道了用甲醛作为合成气替代物的不对称转移氢甲酰化（ATHF）。一种由市售的[Rh(acac)(CO)2] （acac=乙酰丙酮）和1,2-二[(2S,5S)-2,5-二苯基磷酸]乙烷（1,5-环二烯）（Ph-BPE）衍生的催化剂在活性和对映选择性方面都很突出。值得注意的是，该方法不仅可以获得高选择性，而且反应非常简单，而且与使用相同催化剂（或其他主要催化剂）相比，在典型条件下可以获得更高的对映选择性（高达96% ee）和/或周转频率。
As an alternative to conventional asymmetric hydroformylation (AHF), asymmetric transfer hydroformylation (ATHF) by using formaldehyde as a surrogate for syngas is reported. A catalyst derived from commercially available [Rh(acac)(CO)2] (acac=acetylacetonate) and 1,2-bis[(2S,5S)-2,5-diphenylphospholano]ethane(1,5-cyclooctadiene) (Ph-BPE) stands out in terms of both activity and enantioselectivity. Remarkably, not only are high selectivities achievable, the reactions are very simple to perform, and higher enantioselectivity (up to 96 % ee) and/or turnover frequencies than those achievable by using the same catalyst (or other leading catalysts) can be obtained by using typical conditions for AHF.