一类用于水相、镧系金属催化、对映选择性 Mukaiyama 羟醛反应的新型配体。
A new class of ligands for aqueous, lanthanide-catalyzed, enantioselective Mukaiyama aldol reactions.
机构信息
Department of Chemistry, Wayne State University, Detroit, Michigan 48202, USA.
出版信息
J Am Chem Soc. 2010 Sep 22;132(37):12871-3. doi: 10.1021/ja107197p.
Abstract
The development of aqueous methods for generating enantiopure β-hydroxy carbonyl compounds is an important goal because these subunits compose many bioactive compounds and the ability to synthesize these groups in water has environmental and cost benefits. In this communication, we report a new class of ligands for aqueous, lanthanide-catalyzed, asymmetric Mukaiyama aldol reactions for the synthesis of chiral β-hydroxy ketones. Furthermore, we have used luminescence-decay measurements to unveil mechanistic information regarding the catalytic reaction via changes in water-coordination number. The precatalysts presented here yielded β-hydroxy carbonyls from aliphatic and aryl substrates with outstanding syn:anti ratios and enantiometric excesses of up to 49:1 and 97%, respectively.
摘要
开发用于生成对映纯β-羟基羰基化合物的水相方法是一个重要的目标，因为这些亚基构成了许多生物活性化合物，并且在水中合成这些基团具有环境和成本效益。在本通讯中，我们报告了一类用于水相、镧系金属催化的不对称 Mukaiyama 醛醇反应的新型配体，用于合成手性β-羟基酮。此外，我们还通过水配位数的变化，利用荧光衰减测量来揭示催化反应的机理信息。这里提出的前催化剂可以从脂肪族和芳族底物中得到β-羟基羰基化合物，具有出色的 syn:anti 比值和高达 49:1 和 97%的对映体过量。
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