CuH in a bottle: A convenient reagent for asymmetric hydrosilylations
CuH in a bottle: A convenient reagent for asymmetric hydrosilylations
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DOI：
10.1002/anie.200500800
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发表时间：
2005-01-01
影响因子：
16.6
通讯作者：
Frieman, BA
中科院分区：
文献类型：
--
作者：
Lipshutz, BH;Frieman, BA
意义：本研究小组已经证明，与Takasago配体络合的CuH是各种a，b-不饱和羰基化合物的不对称硅氢化反应的极佳试剂。本文描述了一种良好、稳定的“瓶装CUH”，该试剂在1 mm的甲苯溶液中可长时间(长达两个月)保留高对映体选择性。CuH物种的铜源根据反阴离子的不同表现出不同的反应活性。该催化剂在微波反应中表现出较高的转化率和对映体选择性。~1H核磁共振谱显示催化剂(1)的氢化峰位于2.55ppm，与非手性的ph3p配位络合物不同，其氢化峰位于3.52ppm。
Significance: This group has shown that CuH complexed with the Takasago ligand is an excellent reagent for asymmetric hydrosilylation of various a, b-unsaturated carbonyl compounds. This paper describes a nice, stable ‘CuH in a bottle’that provides retention of high enantioselectivities for long storage times (up to two months) of a 1 mM toluene solution of this reagent. The copper source for the CuH species showed different reactivity depending on the counter anion. This catalyst also proved to be robust enough for a microwave reaction showing high conversion and enantioselectivity. The presence of Ph3P was shown to reduce the ee and 1H NMR spectroscopy revealed a catalyst (1) hydride peak at 2.55 ppm that differs from the achiral Ph3P-coordinated complex showing a hydride peak at 3.52 ppm.