Department of Chemistry, Indian Institute of Technology Delhi, Hauz Khas, New Delhi, 110016, India.
Angew Chem Int Ed Engl. 2021 May 3;60(19):10964-10970. doi: 10.1002/anie.202100643. Epub 2021 Mar 18.
We report a strategy to develop heterogeneous single-site enantioselective catalysts based on naturally occurring amino acids and earth-abundant metals for eco-friendly asymmetric catalysis. The grafting of amino acids within the pores of a metal-organic framework (MOF), followed by post-synthetic metalation with iron precursor, affords highly active and enantioselective (>99 % ee for 10 examples) catalysts for hydrosilylation and hydroboration of carbonyl compounds. Impressively, the MOF-Fe catalyst displayed high turnover numbers of up to 10 000 and was recycled and reused more than 15 times without diminishing the enantioselectivity. MOF-Fe displayed much higher activity and enantioselectivity than its homogeneous control catalyst, likely due to the formation of robust single-site catalyst in the MOF through site-isolation.
我们报告了一种基于天然氨基酸和丰富金属开发异质单原子手性催化剂的策略，用于环保不对称催化。在金属-有机骨架（MOF）的孔内接枝氨基酸，然后用铁前体制备后合成金属化，得到高效和高对映选择性（10 个实例中 >99%ee）的催化剂，用于羰基化合物的硅氢化和硼氢化。令人印象深刻的是，MOF-Fe 催化剂的周转数高达 10000，并且在不降低对映选择性的情况下，回收和重复使用超过 15 次。MOF-Fe 比其均相对照催化剂具有更高的活性和对映选择性，这可能是由于在 MOF 中通过位隔离形成了稳定的单原子催化剂。
