Environmental Modulation of Chiral Prolinamide Catalysts for Stereodivergent Conjugate Addition.
Environmental Modulation of Chiral Prolinamide Catalysts for Stereodivergent Conjugate Addition.
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DOI：
10.1016/j.jcat.2022.01.003
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发表时间：
2022-03
影响因子：
7.3
通讯作者：
Zhao Y
中科院分区：
文献类型：
--
作者：
Li X;Zhao Y
合成手性催化剂一般依靠近端官能团或配体进行手性诱导。酶通常利用环境手性来实现立体选择性。环境控制催化具有诸如大小和形状选择性等优点，但尚未得到化学家的充分探索。我们在此报道分子印迹纳米颗粒（MINPs）利用其环境手性来增强或逆转手性脯氨酸酰胺辅助因子的固有选择性。后一种能力使催化剂在乙醛与硝基的共轭加成反应中产生不利的产物。该催化反应在室温下在水中进行，产生的γ-硝基醛收率最高可达94%，ee收率最高可达90%。通过催化剂衍生和环境选择性的结合，可实现高达25:1的syn/anti和1:6的syn/anti比例。MINP的高对映选择性也使得外消旋催化剂可以进行不对称催化，共轭加成的ee高达80%。
Synthetic chiral catalysts generally rely on proximal functional groups or ligands for chiral induction. Enzymes often employ environmental chirality to achieve stereoselectivity. Environmentally controlled catalysis has benefits such as size and shape selectivity but is underexplored by chemists. We here report molecularly imprinted nanoparticles (MINPs) that utilized their environmental chirality to either augment or reverse the intrinsic selectivity of a chiral prolinamide cofactor. The latter ability allowed the catalyst to produce products otherwise disfavored in the conjugate addition of aldehyde to nitroalkene. The catalysis occurred in water at room temperature and afforded γ-nitroaldehydes with excellent yields (up to 94%) and ee (>90% in most cases). Up to 25:1 syn/anti and 1:6 syn/anti ratios were achieved through a combination of catalyst-derived and environmentally enabled selectivity. The high enantioselectivity of the MINP also made it possible for racemic catalysts to perform asymmetric catalysis, with up to 80% ee for the conjugate addition.
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影响因子：
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