Asymmetric hydrogenation of α,β-unsaturated acids catalyzed by noble metals has been well established, whereas, the asymmetric hydrogenation with earth-abundant-metal was rarely reported. Here, we describe a cobalt-catalyzed asymmetric hydrogenation of α,β-unsaturated carboxylic acids. By using chiral cobalt catalyst bearing electron-donating diphosphine ligand, high activity (up to 1860 TON) and excellent enantioselectivity (up to >99% ee) are observed. Furthermore, the cobalt-catalyzed asymmetric hydrogenation is successfully applied to a broad spectrum of α,β-unsaturated carboxylic acids, such as various α-aryl and α-alkyl cinnamic acid derivatives, α-oxy-functionalized α,β-unsaturated acids, α-substituted acrylic acids and heterocyclic α,β-unsaturated acids (30 examples). The synthetic utility of the protocol is highlighted by the synthesis of key intermediates for chiral drugs (6 cases). Preliminary mechanistic studies reveal that the carboxy group may be involved in the control of the reactivity and enantioselectivity through an interaction with the metal centre.

贵金属催化的α，β-不饱和酸的不对称氢化已经被很好地建立，而稀土金属不对称氢化的报道很少。在这里，我们描述了α，β-不饱和羧酸的钴催化不对称氢化。通过使用带有给电子二膦配体的手性钴催化剂，观察到高活性（高达1860 TON）和出色的对映选择性（高达> 99％ee）。此外，钴催化的不对称加氢成功地应用于各种α，β-不饱和羧酸，例如各种α-芳基和α-烷基肉桂酸衍生物，α-氧官能化的α，β-不饱和酸， α-取代的丙烯酸和杂环α，β-不饱和酸（30个例子）。该协议的综合实用性通过手性药物关键中间体的合成得到了强调（6例）。初步的机理研究表明，羧基可能通过与金属中心的相互作用参与反应性和对映选择性的控制。