Practical Organocatalytic Synthesis of Functionalized Non-C2-Symmetrical Atropisomeric Biaryls
Dr. Hongyin Gao
Department of Chemistry, Rice University, BioScience Research Collaborative, 6500 Main Street, Rm 380, Houston, TX 77030 (USA)
These authors contributed equally to this work.
Search for more papers by this authorProf. Dr. Qing-Long Xu
Department of Chemistry, Rice University, BioScience Research Collaborative, 6500 Main Street, Rm 380, Houston, TX 77030 (USA)
Current address: Jiangsu Key Laboratory of Drug Discovery for Metabolic Disease and State Key Laboratory of Natural Medicines China Pharmaceutical University, 24 Tongjia Xiang, Nanjing 210009 (P.R. China)
These authors contributed equally to this work.
Search for more papers by this authorCraig Keene
Department of Chemistry, Rice University, BioScience Research Collaborative, 6500 Main Street, Rm 380, Houston, TX 77030 (USA)
Search for more papers by this authorDr. Muhammed Yousufuddin
Life and Health Sciences Department, The University of North Texas at Dallas, Dallas, TX 75241 (USA)
Search for more papers by this authorProf. Dr. Daniel H. Ess
Department of Chemistry and Biochemistry, Brigham Young University, Provo, UT 84602 (USA)
Search for more papers by this authorCorresponding Author
Prof. Dr. László Kürti
Department of Chemistry, Rice University, BioScience Research Collaborative, 6500 Main Street, Rm 380, Houston, TX 77030 (USA)
Department of Chemistry, Rice University, BioScience Research Collaborative, 6500 Main Street, Rm 380, Houston, TX 77030 (USA)Search for more papers by this authorDr. Hongyin Gao
Department of Chemistry, Rice University, BioScience Research Collaborative, 6500 Main Street, Rm 380, Houston, TX 77030 (USA)
These authors contributed equally to this work.
Search for more papers by this authorProf. Dr. Qing-Long Xu
Department of Chemistry, Rice University, BioScience Research Collaborative, 6500 Main Street, Rm 380, Houston, TX 77030 (USA)
Current address: Jiangsu Key Laboratory of Drug Discovery for Metabolic Disease and State Key Laboratory of Natural Medicines China Pharmaceutical University, 24 Tongjia Xiang, Nanjing 210009 (P.R. China)
These authors contributed equally to this work.
Search for more papers by this authorCraig Keene
Department of Chemistry, Rice University, BioScience Research Collaborative, 6500 Main Street, Rm 380, Houston, TX 77030 (USA)
Search for more papers by this authorDr. Muhammed Yousufuddin
Life and Health Sciences Department, The University of North Texas at Dallas, Dallas, TX 75241 (USA)
Search for more papers by this authorProf. Dr. Daniel H. Ess
Department of Chemistry and Biochemistry, Brigham Young University, Provo, UT 84602 (USA)
Search for more papers by this authorCorresponding Author
Prof. Dr. László Kürti
Department of Chemistry, Rice University, BioScience Research Collaborative, 6500 Main Street, Rm 380, Houston, TX 77030 (USA)
Department of Chemistry, Rice University, BioScience Research Collaborative, 6500 Main Street, Rm 380, Houston, TX 77030 (USA)Search for more papers by this authorGraphical Abstract
An organic acid catalyzed direct arylation of aromatic C(sp2)H bonds in phenols and naphthols was developed. This transformation is operationally simple, does not require an external oxidant, is readily scaled up, and the structurally diverse biaryls are formed with complete regioselectivity. Density functional calculations suggest a mechanism involving a mixed-acetal formation/[3,3]-sigmatropic rearrangement sequence.
Abstract
An organic acid catalyzed direct arylation of aromatic C(sp2)H bonds in phenols and naphthols for the preparation of 1,1′-linked functionalized biaryls was developed. The products are non-C2-symmetrical, atropoisomeric, and represent previously untapped chemical space. Overall this transformation is operationally simple, does not require an external oxidant, is readily scaled up (up to 98 mmol), and the structurally diverse 2,2′-dihydroxy biaryl (i.e., BINOL-type), as well as 2-amino-2′-hydroxy products (i.e., NOBIN-type) are formed with complete regioselectivity. Density-functional calculations suggest that the quinone and imino-quinone monoacetal coupling partners are exclusively arylated at their α-position by an asynchronous [3,3]-sigmatropic rearrangement of a mixed acetal species which is formed in situ under the reaction conditions.
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