Synlett, Table of Contents Synlett 2022; 33(07): 694-698DOI: 10.1055/a-1770-7922 letter Bismuth(III) Triflate-Catalyzed Intermolecular Cyclization of Phenols with Diols: Direct Access to O-Heterocycles Authors Maki Minakawa∗ Yuya Sakurai Recommend Article Abstract Buy Article(opens in new window) All articles of this category(opens in new window) Abstract A direct access to O-heterocycles by Bi(OTf)3-catalyzed intermolecular cyclization of phenols with diols is described. Catalytic dehydrative tandem formation of C–O and C–C bonds was achieved by using a Bi(OTf)3 catalyst without any additives. The catalytic intermolecular cyclization of phenols with various diols proceeded to give the corresponding chromanes in up to 91% yield and/or pyran derivatives in up to 66% yield. Key words Key wordsphenols - diols - bismuth catalysis - cyclization - chromanes - pyrans Full Text References References and Notes 1a Kaur N. Metal and Nonmetal Assisted Synthesis of Six-Membered Heterocycles. 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The resulting mixture was purified by preparative TLC (Wakogel B-5F, hexane–EtOAc, 10:1) to give an orange solid; yield: 2.0 mg (23%); mp 185.8–187.6 °C. 1H NMR (600 MHz, CDCl3): δ = 2.13–2.17 (m, 4 H), 3.05 (t, J = 6.3 Hz, 4 H), 4.23 (t, J = 5.4 Hz, 4 H), 7.05 (d, J = 9.6 Hz, 2 H), 7.60 (d, J = 9.0 Hz, 2 H). 13C{1H} NMR (150 MHz, CDCl3): δ = 21.5 (2 C), 22.4 (2 C), 66.0 (2 C), 114.8 (2 C), 119.0 (2 C), 121.4 (2 C), 128.3 (2 C), 150.8 (2 C). HRMS (EI): m/z [M+] calcd for C16H16O2: 240.1150; found: 240.1186. 7 The reaction of methyl-branched diols 2b–f with 1-naphthol (1a) in the presence of Bi(OTf)3 catalyst gave cyclized products in 54% yield, even at 90 °C. The stability of the cationic species derived from diols might affect the cyclization reaction. 8 Leleti RR, Hu B, Prashad M, Repič O. Tetrahedron Lett. 2007; 48: 8505 For syntheses of ethers by Bi(OTf)3 catalysis, see: 9a Murai M, Origuchi K, Takai K. Org. Lett. 2014; 16: 3828 9b Ollevier T, Mwene-Mbeja TM. 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