Preparation of Optically Active 2,2'-Dibromo-6,6'-diiodo-1,1'-biphenyl: A Powerful Precursor for Modular Synthesis of Functionalized Atropisomers†
Yuanyuan Li
Hefei National Research Center for Physical Sciences at the Microscale and Department of Chemistry, University of Science and Technology of China, 96 Jinzhai Road, Hefei, Anhui, 230026 China
Search for more papers by this authorLonghui Duan
Hefei National Research Center for Physical Sciences at the Microscale and Department of Chemistry, University of Science and Technology of China, 96 Jinzhai Road, Hefei, Anhui, 230026 China
Search for more papers by this authorBiqiong Hong
College of Materials and Chemical Engineering, Minjiang University, Fuzhou, Fujian, 350108 China
Search for more papers by this authorCorresponding Author
Zhenhua Gu
Hefei National Research Center for Physical Sciences at the Microscale and Department of Chemistry, University of Science and Technology of China, 96 Jinzhai Road, Hefei, Anhui, 230026 China
College of Materials and Chemical Engineering, Minjiang University, Fuzhou, Fujian, 350108 China
E-mail: [email protected]Search for more papers by this authorYuanyuan Li
Hefei National Research Center for Physical Sciences at the Microscale and Department of Chemistry, University of Science and Technology of China, 96 Jinzhai Road, Hefei, Anhui, 230026 China
Search for more papers by this authorLonghui Duan
Hefei National Research Center for Physical Sciences at the Microscale and Department of Chemistry, University of Science and Technology of China, 96 Jinzhai Road, Hefei, Anhui, 230026 China
Search for more papers by this authorBiqiong Hong
College of Materials and Chemical Engineering, Minjiang University, Fuzhou, Fujian, 350108 China
Search for more papers by this authorCorresponding Author
Zhenhua Gu
Hefei National Research Center for Physical Sciences at the Microscale and Department of Chemistry, University of Science and Technology of China, 96 Jinzhai Road, Hefei, Anhui, 230026 China
College of Materials and Chemical Engineering, Minjiang University, Fuzhou, Fujian, 350108 China
E-mail: [email protected]Search for more papers by this authorDedicated to the Memory of Professor Xiyan Lu.
Comprehensive Summary
The widespread applications of atropisomeric compounds have led to an increasing demand for their synthesis. Rather than synthesizing different functionalized atropisomers individually, an attractive alternative is to identify a key intermediate or precursor that can be readily elaborated and functionalized to realize divergent synthesis of this class of compounds. Building on our previous research on asymmetric ring-opening of cyclic diaryliodoniums, in this work we developed a copper-catalyzed enantioselective ring-opening reaction of ortho,ortho’-dibromo substituted cyclic diaryliodonium with lithium iodide. The resulting optically active product 2,2'-dibromo-6,6'-diiodo-1,1'-biphenyl, possessing two C—Br bonds and two C—I bonds, can be selectively advanced to form different functionalities. Remarkably, the utilities of the product were highlighted by successively demonstrating C—I and C—Br metalation, followed by carboxylation, boroylation, oxygenation, allylation, phosphinylation, etc., all of which provide a new and convenient approach to synthesizing a range of functionalized axially chiral biphenyls.
Supporting Information
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