Nickel-Catalyzed Decarbonylation of α-Oxyacetic Acid Thioesters: Hydroxymethylation of Mercaptans

Abstract

A strategy for the Ni-catalyzed decarbonylation of α-oxyacetic acid thioesters is described, providing a new pathway for the synthesis of monosulfide acetals, and further proving that oxygen atoms can stabilize an α-carbocation and promote a decarbonylation reaction. This method has good functional-group compatibility and can tolerate a wide range of electron-withdrawing, electron-neutral, and electron-donating substituents. In addition, this method complements the conventional cross-coupling reactions.

Key words

decarbonylation - rearrangement - nickel catalysis - C–S bond - monothioacetals

• References and Notes

• 1 Pan F, Shi Z.-J. ACS Catal. 2014; 4: 280
• 2 Liu C, Szostak M. ChemCatChem 2021; 13: 4878
• 3 Beletskaya IP, Ananikov VP. Chem. Rev. 2011; 111: 1596
• 4 Chauhan P, Mahajan S, Enders D. Chem. Rev. 2014; 114: 8807
• 5 Guo S.-r, Yuan Y.-q, Xiang J.-n. Org. Lett. 2013; 15: 4654
• 6 Zhu X, Xie X, Li P, Guo J, Wang L. Org. Lett. 2016; 18: 1546
• 7 Liu C, Szostak M. Chem. Commun. 2018; 54: 2130
• 8 Brigham CE, Malapit CA, Lalloo N, Sanford MS. ACS Catal. 2020; 10: 8315
• 9 Zhou J.-Y, Tian R, Zhu Y.-M. J. Org. Chem. 2021; 86: 12148
• 10 Zheng Z.-J, Jiang C, Shao P.-C, Liu W.-F, Zhao T.-T, Xu P.-F, Wei H. Chem. Commun. 2019; 55: 1907
• 11 Tian R, Li J.-X, Zhu Y.-M. Tetrahedron 2023; 139: 133437
• 12 Zhou J.-Y, Tao S.-W, Liu R.-Q, Zhu Y.-M. J. Org. Chem. 2019; 84: 11891
• 13a Cao H, Liu X, Bie F, Shi Y, Han Y, Yan P, Liu C. Org. Chem. Front. 2021; 8: 1587
• 13b Ding K, Xu S, Alotaibi R, Paudel K, Reinheimer EW, Weatherly J. J. Org. Chem. 2017; 82: 4924
• 14a Lautens M, Marchese AD. Synfacts 2020; 16: 679
• 14b Malapit CA, Borrell M, Milbauer MW, Brigham CE, Sanford MS. J. Am. Chem. Soc. 2020; 142: 5918
• 14c Qin T, Malins LR, Edwards JT, Merchant RR, Novak AJ, Zhong J.-Z, Baran PS. Angew. Chem. Int. Ed. 2017; 56: 260
• 15a Yue H, Guo L, Lee S.-C, Liu X, Rueping M. Angew. Chem. Int. Ed. 2017; 56: 3972
• 15b Chen Q, Fu L, You J, Nishihara Y. Synlett 2021; 32: 1560
• 16 Takise R, Isshiki R, Muto K, Itami K, Yamaguchi J. J. Am. Chem. Soc. 2017; 139: 3340
• 17 Lu H, Yu T.-Y, Xu P.-F, Wei H. Chem. Rev. 2020; 121: 365
• 18 Guo L, Rueping M. Acc. Chem. Res. 2018; 51: 1185
• 19a Muto K, Yamaguchi J, Musaev DG, Itami K. Nat. Commun. 2015; 6: 7508
• 19b Cao D, Ataya M, Chen Z, Zeng H, Peng Y, Khaliullin RZ, Li C.-J. Nat. Commun. 2022; 13: 1805
• 20 Thioethers 2a–t; General Procedure A 15 mL sealed tube equipped with a magnetic stirrer bar was charged with the appropriate thioester 1 (0.5mmol), NiCl₂ (0.05 mmol, 7 mg), dppe (0.1 mmol, 40 mg), Na₂CO₃ (0.1mmol, 11 mg), Mn (0.25 mmol, 14 mg), and anhyd toluene (1.0 mL). The tube was purged with nitrogen, and the contents were stirred at 170 °C for 24 h. When the reaction was complete, the mixture was filtered through a pad of Celite and the solvents were removed under reduced pressure. The residue was purified by column chromatography [silica gel, PE–EtOAc (500:1)]. 2-(4-Toluenesulfanyl)tetrahydrofuran (2a) Colorless liquid; yield: 81 mg (83%). ¹H NMR (300 MHz, CDCl₃): δ = 7.42 (d, J = 7.9 Hz, 2 H), 7.12 (d, J = 7.5 Hz, 2 H), 5.59 (dd, J = 7.1, 3.6 Hz, 1 H), 4.12–3.89 (m, 2 H), 2.34 (d, J = 3.5 Hz, 4 H), 2.05–1.79 (m, 3 H). ¹³C NMR (101 MHz, CDCl₃): δ = 137.0, 131.9, 131.8, 129.6, 87.6, 67.2, 32.6, 24.9, 21.1. 2-(4-Fluorophenylsulfanyl)tetrahydrofuran (2f) Colorless liquid; yield: 65 mg (66%). ¹H NMR (300 MHz, CDCl₃): δ = 7.41 (s, 2 H), 6.91 (d, J = 10.2 Hz, 2 H), 5.45 (s, 1 H), 3.89 (d, J = 15.5 Hz, 2 H), 2.26 (s, 1 H), 1.90 (s, 3 H). ¹³C NMR (101 MHz, CDCl₃): δ = 162.4 (d, J = 246.9 Hz), 134.0 (d, J = 8.0 Hz), 130.5 (d, J = 3.3 Hz), 115.9 (d, J = 21.7 Hz), 87.8, 67.2, 32.6, 24.8. 2-(4-Toluenesulfanyl)tetrahydro-2H-pyran (2p) Colorless liquid; yield: 49 mg (47%). ¹H NMR (300 MHz, CDCl₃): δ = 7.42 (d, J = 7.8 Hz, 2 H), 7.14 (d, J = 7.7 Hz, 2 H), 5.16 (dd, J = 6.0, 3.8 Hz, 1 H), 4.21 (dt, J = 10.3, 4.7 Hz, 1 H), 3.60 (dt, J = 11.0, 5.0 Hz, 1 H), 2.36 (s, 3 H), 2.10–1.97 (m, 1 H), 1.86 (dtt, J = 13.2, 6.2, 3.4 Hz, 2 H), 1.68–1.62 (m, 3 H). ¹³C NMR (101 MHz, CDCl₃): δ = 137.0, 131.7, 131.4, 129.6, 85.7, 64.6, 31.6, 25.6, 21.7, 21.1. 1-[(tert-Butoxymethyl)sulfanyl]-4-methylbenzene (2q) Colorless liquid; yield: 71 mg (68%). ¹H NMR (300 MHz, CDCl₃): δ = 7.31 (d, J = 7.8 Hz, 2 H), 7.02 (d, J = 8.0 Hz, 2 H), 4.78 (d, J = 2.3 Hz, 2 H), 2.24 (s, 3 H), 1.16 (s, 9 H). ¹³C NMR (101 MHz, CDCl₃): δ = 136.6, 132.8, 130.7, 129.6, 75.2, 68.8, 27.9, 21.1.