Xiong Qi, Xiao Lu, Dong Xiu-Qin, Wang Chun-Jiang
Engineering Research Center of Organosilicon Compounds & Materials, Ministry of Education, College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, China.
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Shanghai 230021, China.
Org Lett. 2022 Apr 8;24(13):2579-2584. doi: 10.1021/acs.orglett.2c00942. Epub 2022 Mar 28.
Iridium-catalyzed cascade allylation/macrolactonization between vinylethylene carbonate (VEC) and isatoic anhydride derivatives was successfully developed, readily generating a wide range of -symmetric chiral macrodiolides bearing 14-membered rings in moderate to good yields with excellent diastereoselectivities and enantioselectivities (generally 99% ee). Control experiments revealed that racemic VEC as the precursor of electrophilic iridium-π-allyl species underwent kinetic resolution process. This expedient protocol features easily available substrates, excellent stereoselective control, and high step economy.
成功开发了铱催化的碳酸亚乙烯酯（VEC）与异吲哚酮酸酐衍生物之间的串联烯丙基化/大环内酯化反应，该反应能够轻松地以中等至良好的产率生成多种含有14元环的对称手性大环二内酯，具有出色的非对映选择性和对映选择性（通常ee值为99%）。对照实验表明，作为亲电铱-π-烯丙基物种前体的外消旋VEC经历了动力学拆分过程。该便捷方法具有底物易于获得、出色的立体选择性控制和高步骤经济性等特点。
