文献类型：期刊文献

英文题名：Building inherently chiral icosahedral-carborane-fused boron

作者：Guo, Hong-Can;Yao, Bo-Xuan;Liu, Hui-Chong[1];He, Dongyang[5];Cheng, Zhe[1];Wang, Ruo-Xuan[1];Zhou, Zikang[1];Guo, Hong[1];Tang, Wenjun[2,3];Ni, Shao-Fei[2,3,4];Mu, Xin[1]

机构：[1]East China Univ Sci & Technol, Engn Res Ctr Pharmaceut Proc Chem, Sch Pharm, Minist Educ, 130 Meilong Rd, Shanghai 200237, Peoples R China;[2]Shantou Univ, Coll Dept Chem, Shantou 515063, Peoples R China;[3]Shantou Univ, Key Lab Preparat & Applicat Ordered Struct Mat Gua, Shantou 515063, Peoples R China;[4]Chem & Chem Engn Guangdong Lab, Shantou 515063, Peoples R China;[5]Univ Chinese Acad Sci, Shanghai Inst Organ Chem, State Key Lab Chem Biol, 345 Ling Ling Rd, Shanghai 200032, Peoples R China

年份：2025

卷号：6

期号：9

外文期刊名：CELL REPORTS PHYSICAL SCIENCE

收录：;WOS:【SCI-EXPANDED(收录号:WOS:001576909500005)】；

基金：We are grateful for financial support from the Natural Science Foundation of Shanghai (22ZR1416700) and the Engineering Research Center of Pharma-ceutical Process Chemistry, Ministry of Education. S.-F.N. is thankful for finan-cial support from the Guangdong Basic and Applied Basic Research Founda-tion (2024A1515010323) and the open research fund of Songshan Lake Materials Laboratory (2023SLABFN16) . We thank Dr. Chuanqi Hou from the Shanghai Institute of Organic Chemistry for his assistance in chiral HPLC anal-ysis. We thank Dr. Xiao-Long Wan from the Shanghai Institute of Organic Chemistry for assistance in CD spectra measurement. We thank Dr. Prof. Alex-ander Spokoyny from the University of California, Los Angeles, and Dr. Prof. Zuxiao Zhang from the University of Hawai'i at Manoa for insightful discussions.

语种：英文

摘要：In this article, we present an asymmetric synthesis of inherently chiral carborane-fused boraphenanthrenes. The introduction of axially chiral biaryl moieties can facilitate stereoselective oxidative cyclization to generate carborane-fused boraphenanthrene moieties. In this transformation, aryl groups were first installed on the carborane's vicinal boron vertices. Following regioselective bromination at the sterically hindered aryl C-H bond, the asymmetric cross-coupling reactions produced the axially chiral biaryls adjacent to the carborane. The final intramolecular oxidative-cyclization-induced chiral transfer involving two vicinal aryl groups resulted in the generation of non-coplanar carborane-fused boraphenanthrene analogs. The stereochemistry of axial biaryls is crucial for determining the configuration of twisted carborane-fused boraphenanthrenes. Notably, during the oxidative cyclization, a formal 1,2-carboranyl transposition was observed. These results represent the first example, to our knowledge, of a 1,2-B-C(sp2) bond migration reaction. Initial photophysical studies reveal a significant redshift in the photoluminescence spectra of the products compared to the uncyclized substrates.