학술논문
Sigmatropic Rearrangements of Hypervalent-Iodine-Tethered Intermediates for the Synthesis of Biaryls.
Document Type
Academic Journal
Author
Hori M; Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto, 606-8502, Japan.; Guo JD; Institute for Chemical Research, Kyoto University, Gokasho, Uji, Kyoto, 611-0011, Japan.; Yanagi T; Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto, 606-8502, Japan.; Nogi K; Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto, 606-8502, Japan.; Sasamori T; Graduate School of Natural Sciences, Nagoya City University, Yamanohata 1, Mizuho-cho, Mizuho-ku, Nagoya, Aichi, 467-8501, Japan.; Yorimitsu H; Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto, 606-8502, Japan.
Source
Publisher: Wiley-VCH Country of Publication: Germany NLM ID: 0370543 Publication Model: Print-Electronic Cited Medium: Internet ISSN: 1521-3773 (Electronic) Linking ISSN: 14337851 NLM ISO Abbreviation: Angew Chem Int Ed Engl Subsets: PubMed not MEDLINE
Subject
Language
English
Abstract
Metal-free dehydrogenative couplings of aryliodanes with phenols to afford 2-hydroxy-2'-iodobiaryls have been developed. This reaction proceeds through ligand exchange on the hypervalent iodine atom followed by a [3,3] sigmatropic rearrangement and with complete regioselectivity. This coupling, in combination with in situ oxidation by mCPBA, enables the convenient conversion of iodoarenes into desirable biaryls. The obtained biaryls have convertible iodo and hydroxy groups in close proximity, and are thus synthetically useful, as exemplified by the controlled syntheses of π-extended furans and a substituted [5]helicene. DFT calculations clearly revealed that the rearrangement is sigmatropic, with C-C bond formation and I-O bond cleavage proceeding in a concerted manner. Acetic acid, which was found to be the best solvent for this protocol, renders the iodine atom more cationic and thus accelerates the sigmatropic rearrangement.
(© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)
(© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)