Bismuth(III) Triflate-Catalyzed Intermolecular Cyclization of Phenols with Diols: Direct Access to O-Heterocycles

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

phenols - diols - bismuth catalysis - cyclization - chromanes - pyrans

Publication History

Received: 20 January 2022

Accepted after revision: 14 February 2022

Accepted Manuscript online:
14 February 2022

Article published online:
10 March 2022

• References and Notes

• 1a Kaur N. Metal and Nonmetal Assisted Synthesis of Six-Membered Heterocycles. Elsevier; Amsterdam: 2020: 295
• 1b Shen HC. Tetrahedron 2009; 65: 3931
• 1c Spasov AA, Babkov DA, Osipov DV, Klochkov VG, Prilepskaya DR, Demidov MR, Osyanin VA, Klimochkin YN. Bioorg. Med. Chem. Lett. 2019; 29: 119
• 1d Moorthy JN, Venkatakrishnan P, Samanta S, Kumar DK. Org. Lett. 2007; 9: 919
• 1e Macone A, Lendaro E, Comandini A, Rovardi I, Matarese RM, Carraturo A, Bonamore A. Bioorg. Med. Chem. 2009; 17: 6003
• 2a Claisen L. Ber. Dtsch. Chem. Ges. 1921; 54: 200
• 2b Smith LI, Ungnade HE, Hoehn HH. Wawzonek S. J. Org. Chem. 1939; 4: 311
• 2c Bader AR, Bean WC. J. Am. Chem. Soc. 1958; 80: 3073
• 2d Dewhirst KC, Rust FF. J. Org. Chem. 1963; 28: 798
• 2e Bolzoni L, Casiraghi G, Casnati G, Sartori G. Angew. Chem., Int. Ed. Engl. 1978; 17: 684
• 2f Ahluwalia VK, Arora KK. Tetrahedron 1981; 37: 1437
• 3a Adro LA, Hii KK. Chem. Commun. 2008; 2325
• 3b Youn SW, Eom JI. J. Org. Chem. 2006; 71: 6705
• 3c Youn SY. Synlett 2007; 3050
• 3d Dang TT, Boeck F, Hintermann L. J. Org. Chem. 2011; 76: 9353
• 4a Dintzner MR, McClelland KM, Morse KM, Akroush MH. Synlett 2004; 2028
• 4b Yamamoto Y, Itonaga K. Org. Lett. 2009; 11: 717
• 4c Vece V, Ricci J, Poullain-Martini S, Nava P, Carissan Y, Humbel S, Duñach E. Eur. J. Org. Chem. 2010; 6239
• 5a Minakawa M, Minami K, Sato Y. Synlett 2021; 32: 1869
• 5b Minakawa M, Watanabe K, Toyoda S, Uozumi Y. Synlett 2018; 29: 2385
• 6 2,3,4,8,9,10-Hexahydrochromeno[6,5-f]chromene (3ca); Typical Procedure A vial was charged with 2-naphthol (1b: 16.4 mg, 0.1 mmol), Bi(OTf)₃ (3.3 mg, 5.0 mol%), propane-1,3-diol (2a: 156.4 mg, 2.0 mmol), and mesitylene (0.1 mL) under N₂, and the mixture was stirred at 180 °C for 17 h. 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. Tetrahedron Lett. 2006; 47: 4051
• 9c Steedhar B, Swapna V, Sridhar C. Synth. Commun. 2004; 34: 1433
• 9d Orita A, Tanahashi C, Kakuda A, Otera J. Angew. Chem. Int. Ed. 2000; 39: 2877
• 9e Orita A, Tanahashi C, Kakuda A, Otera J. J. Org. Chem. 2001; 66: 8926

For acid-catalyzed 1,3-shifts, see:
• 10a Lutz RP. Chem. Rev. 1984; 84: 205
• 10b Dauben WG, Cogen JM, Behar V. Tetrahedron Lett. 1990; 31: 3241
• 10c Maruoka K, Sato J, Banno H, Yamamoto H. Tetrahedron Lett. 1990; 31: 377
• 10d Talamás FX, Smith DB, Cervantes A, Franco F, Cutler ST, Loughhead DG, Morgans DJ. Jr, Weikert RJ. Tetrahedron Lett. 1997; 38: 4725
• 10e Hoarau C, Pettus TR. R. Synlett 2003; 127
• 10f Dintzner MR, Morse KM, McClelland KM, Coligado DM. Tetrahedron Lett. 2004; 45: 79
• 10g Hui Z, Jiang S, Qi X, Ye X.-Y, Xie T. Tetrahedron Lett. 2020; 61: 151995
• 11 For Bi(OTf)3-catalyzed 1,3-shifts, see: Yadav, J. S.; Reddy, B. V. S.; Swamy, T. Tetrahedron Lett. 2003, 44, 4861; see also ref. 9c.
• 12 For acid-catalyzed cyclization, see: Varghese S, Anand C, Dhawale D, Mane G, Wahab MA, Mano A, Raj GA. G, Nagarajan S, Vinu A. ChemCatChem 2013; 5: 899
• 13 For an example of a π-allylbismuth(III) intermediate, see: Pan Y, Shao Y, Wang J, Liu Z, Chen L, Li X. ACS Catal. 2021; 11: 13752

For Bi(OTf)₃-catalyzed cyclizations, see:
• 14a Komeyama K, Takahashi K, Takai K. Org. Lett. 2008; 10: 5119
• 14b Godeau J, Olivero S, Antoniotti S, Duñach E. Org. Lett. 2011; 13: 3320
• 14c Lemière G, Cacciuttolo B, Belhassen E, Duñach E. Org. Lett. 2012; 14: 2750
• 14d Ondet P, Joffrin A, Diaf I, Lemière G, Duñach E. Org. Lett. 2015; 17: 1002