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- Title
Sigmatropic Rearrangements of Hypervalent‐Iodine‐Tethered Intermediates for the Synthesis of Biaryls.
- Authors
Hori, Mitsuki; Guo, Jing‐Dong; Yanagi, Tomoyuki; Nogi, Keisuke; Sasamori, Takahiro; Yorimitsu, Hideki
- Abstract
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 <italic>m</italic>CPBA, 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.
- Subjects
SIGMATROPIC rearrangements; HYPERVALENCE (Theoretical chemistry); INTERMEDIATES (Chemistry); DEHYDROGENATION; REGIOSELECTIVITY (Chemistry); IODINE; CHEMICAL synthesis
- Publication
Angewandte Chemie, 2018, Vol 130, Issue 17, p4753
- ISSN
0044-8249
- Publication type
Article
- DOI
10.1002/ange.201801132