Regioselective and Enantioselective Hydroformylation of Dialkylacrylamides
Regioselective and Enantioselective Hydroformylation of Dialkylacrylamides
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DOI：
10.1002/adsc.200900871
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发表时间：
2010-04-01
影响因子：
5.4
通讯作者：
Clarke, Matthew L.
中科院分区：
文献类型：
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作者：
Noonan, Gary M.;Newton, David;Clarke, Matthew L.
二甲基丙烯酰胺可以以非常高的化学选择性和区域选择性加氢甲酰化。该底物的不对称水解是可能的，只要采取步骤以使醛产物的外消旋化最小化，并且这项工作证明了各种条件和变量对外消旋化的影响。使用Landis二氮磷杂环戊烷配体，在非常温和的条件下可以实现高达68%ee。其他二烷基丙烯酰胺也在温和条件下加氢甲酰化，得到类似或更好的对映体选择性，包括丙烯酸的Weinreb酰胺（71%ee），和二乙基丙烯酰胺的不对称加氢，产生高达82%ee的手性醛。
Dimethylacrylamide can be hydroformylated with very high chemo- and regioselectivity. Asymmetric hydroformylation of this substrate is possible, provided steps are taken to minimise racemisation of the aldehyde products, and this work demonstrates the effect of various conditions and variables on racemisation. Using the Landis diazaphospholane ligands up to 68% ee can be realised under very mild conditions. Other dialkylacrylamides were also hydroformylated under mild conditions giving similar or better enantioselectivities, including the Weinreb amide of acrylic acid (71% ee), and the asymmetric hydroformylation of diethylacrylamide producing the chiral aldehyde with up to 82% ee.