Guo Qianling, Xie Chaochao, Zi Guofu, Hou Guohua
Key Laboratory of Radiopharmaceuticals, College of Chemistry, Beijing Normal University, Beijing 100875, China.
Org Lett. 2024 Oct 18;26(41):8702-8707. doi: 10.1021/acs.orglett.4c02932. Epub 2024 Oct 3.
The enantioselective synthesis of chiral 4-substituted 4,5-dihydro-1-[1,5]benzodiazepin-2(3)-ones via asymmetric hydrogenation catalyzed by the Pd/f-spiroPhos complex in the presence of hydrochloric acid as an additive has been developed, achieving excellent enantioselectivities and high turnover numbers, up to 99% ee and TON = 4600. More significantly, the asymmetric reductive amination of β-keto esters with 1,2-phenylenediamine has also been successfully realized to afford chiral 4-substituted 4,5-dihydro-1-[1,5]benzodiazepin-2(3)-ones with comparable enantioselectivities of up to 99% ee.
已开发出在盐酸作为添加剂存在下，通过钯/ f-螺环膦络合物催化的不对称氢化反应对映选择性合成手性4-取代的4,5-二氢-1-[1,5]苯并二氮杂卓-2(3)-酮的方法，实现了优异的对映选择性和高转化数，对映体过量高达99%，转化数 = 4600。更重要的是，β-酮酯与1,2-苯二胺的不对称还原胺化反应也已成功实现，可提供对映选择性相当、对映体过量高达99%的手性4-取代的4,5-二氢-1-[1,5]苯并二氮杂卓-2(3)-酮。
