Palladium-Catalyzed Enantioselective 7-exo-Trig Carbopalladation/Carbonylation: Cascade Reactions To Achieve Atropisomeric Dibenzo[b,d]azepin-6-ones

• DOI: 10.1021/acs.orglett.1c01036
• Publication Date: 2021-04-23T02:40:08Z
• Authors: Huaanzi Hu; Yan Peng; Ting Yu; Sidi Cheng; Shuang Luo; Qiang Zhu
• Keywords: 01 natural sciences; 0104 chemical sciences

Enantioselective 7-exo-trig cyclocarbopalladation-initiated carbonylation cascade reactions, leading to seven-membered dibenzo[b,d]azepin-6-ones containing a thermodynamically controlled stereogenic axis, have been realized for the first time. A series of 7-acetate- or 7-acetamide-substituted dibenzo[b,d]azepin-6-ones are obtained under atmospheric pressure of CO in good yields with excellent diastereo- and enantioselectivities. The calculated energy difference between the diastereoisomers generated from the stereogenic biaryl axis and the stereogenic center is approximately 2.8 kcal/mol, which agrees with the excellent diastereoselectivity observed.