Li Xiaorui, Kong Lingyu, Yin Shuxin, Zhou Hengrui, Lin Aijun, Yao Hequan, Gao Shang
State Key Laboratory of Natural Medicines (SKLNM) and Department of Medicinal Chemistry, School of Pharmacy, China Pharmaceutical University, Nanjing, 210009, P. R. China.
Adv Sci (Weinh). 2024 Jun;11(24):e2309706. doi: 10.1002/advs.202309706. Epub 2024 Apr 11.
Palladium-catalyzed Suzuki-Miyaura (SM) coupling is a valuable method for forming C─C bonds, including those between aryl moieties. However, achieving atroposelective synthesis of axially chiral styrenes via SM coupling remains challenging. In this study, a palladium-catalyzed atroposelective Suzuki-Miyaura coupling between gem-diborylalkenes and aryl halides is presented. Using the monophosphine ligand Me-BI-DIME (L2), a range of axially chiral tetra-substituted acyclic styrenes with high yields and excellent enantioselectivities are successfully synthesized. Control experiments reveal that the gem-diboryl group significantly influences the product enantioselectivities and the coupling prefers to occur at sites with lower steric hindrance. Additionally, the alkenyl boronate group in the products proves versatile, allowing for various transformations while maintaining high optical purities.
钯催化的铃木-宫浦（SM）偶联反应是形成碳-碳键（包括芳基部分之间的碳-碳键）的一种有价值的方法。然而，通过SM偶联反应实现轴手性苯乙烯的对映选择性合成仍然具有挑战性。在本研究中，报道了一种钯催化的偕二硼基烯烃与芳基卤化物之间的对映选择性铃木-宫浦偶联反应。使用单膦配体Me-BI-DIME（L2），成功合成了一系列具有高产率和优异对映选择性的轴手性四取代无环苯乙烯。对照实验表明，偕二硼基对产物的对映选择性有显著影响，且偶联反应更倾向于在空间位阻较小的位点发生。此外，产物中的烯基硼酸酯基团具有多种用途，在保持高光学纯度的同时允许进行各种转化。
