Ligand-Free Nickel-Catalyzed Reductive Allylic Defluorinative Cross-Coupling of α-Trifluoromethyl Alkenes with Epoxides

Abstract

We report a reductive allylic defluorinative reaction of α-trifluoromethyl alkenes with terminal epoxides, which consists of an iodide-mediated regioselective ring opening and a nickel-catalyzed radical-type cross-coupling, providing diverse tertiary gem-difluorobishomoallylic alcohols in moderate to high yields. Notably, this reaction is conducted under mild conditions and requires no external ligand or proton donor.

Key words

nickel catalysis - epoxides - difluoroalkenes - defluorination - ring opening

Publikationsverlauf

Eingereicht: 05. Mai 2020

Angenommen: 01. Juni 2020

Artikel online veröffentlicht:
01. Juli 2020

• References and Notes

• 1a Meanwell NA. J. Med. Chem. 2011; 54: 2529
• 1b Magueur G, Crousse B, Ourévitch M, Bonnet-Delpon D, Bégué J.-P. J. Fluorine Chem. 2006; 127: 637
• 2a Bobek M, Kavai I, De Clercq E. J. Med. Chem. 1987; 30: 1494
• 2b Pan Y, Qiu J, Silverman RB. J. Med. Chem. 2003; 46: 5292
• 2c Altenburger J.-M, Lassalle GY, Matrougui M, Galtier D, Jetha J.-C, Bocskei Z, Berry CN, Lunven C, Lorrain J, Herault J.-P, Schaeffer PE, O’Connor S, Herbert J.-M. Bioorg. Med. Chem. 2004; 12: 1713
• 2d Messaoudi S, Treguier B, Hamze A, Provot O, Peyrat J.-F, De Losada JR, Liu J.-M, Bignon J, Wdzieczak-Bakala J, Thoret S, Dubois J, Brion J.-D, Alami M. J. Med. Chem. 2009; 52: 4538

For reviews on the synthesis of gem -difluoroalkenes and their applications in organic synthesis, see:
• 3a Ichikawa J. J. Fluorine Chem. 2000; 105: 257
• 3b Chelucci G. Chem. Rev. 2012; 112: 1344
• 3c Zhang X, Cao S. Tetrahedron Lett. 2017; 58: 375
• 4a Nowak R, Robins MJ. Org. Lett. 2005; 7: 721
• 4b Zhao Y, Huang W, Zhu L, Hu J. Org. Lett. 2010; 12: 1444
• 4c Zheng J, Lin J.-H, Cai J, Xiao J.-C. Chem. Eur. J. 2013; 19: 15261
• 4d Zheng J, Cai J, Lin J.-H, Guo Y, Xiao J.-C. Chem. Commun. 2013; 49: 7513
• 4e Thomoson CS, Martinez H, Dolbier WR. Jr. J. Fluorine Chem. 2013; 150: 53
• 4f Hu M, He Z, Gao B, Li L, Ni C, Hu J. J. Am. Chem. Soc. 2013; 135: 17302
• 4g Li Q, Lin J.-H, Deng Z.-Y, Zheng J, Cai J, Xiao J.-C. J. Fluorine Chem. 2014; 163: 38
• 4h Gao B, Zhao Y, Hu M, Ni C, Hu J. Chem. Eur. J. 2014; 20: 7803
• 4i Wang X.-P, Lin J.-H, Xiao J.-C, Zheng X. Eur. J. Org. Chem. 2014; 2014: 928
• 4j Aikawa K, Toya W, Nakamura Y, Mikami K. Org. Lett. 2015; 17: 4996
• 4k Gao B, Zhao Y, Hu J, Hu J. Org. Chem. Front. 2015; 2: 163
• 4l Hu M, Ni C, Li L, Han Y, Hu J. J. Am. Chem. Soc. 2015; 137: 14496
• 4m Zheng J, Lin J.-H, Yu L.-Y, Wei Y, Zheng X, Xiao J.-C. Org. Lett. 2015; 17: 6150
• 4n Zhang Z, Yu W, Wu C, Wang C, Zhang Y, Wang J. Angew. Chem. Int. Ed. 2016; 55: 273
• 4o Krishnamoorthy S, Kothandaraman J, Saldana J, Prakash GK. S. Eur. J. Org. Chem. 2016; 2016: 4965
• 4p Zeng J.-L, Zhang Y, Zheng M.-M, Zhang Z.-Q, Xue X.-S, Zhang F.-G, Ma J.-A. Org. Lett. 2019; 21: 8244
• 4q Wang S, Cheng B.-Y, Sršen M, König B. J. Am. Chem. Soc. 2020; 142: 7524
• 5a Hiyama T, Obayashi M, Sawahata M. Tetrahedron Lett. 1983; 24: 4113
• 5b Fuchikami T, Shibata Y, Suzuki Y. Tetrahedron Lett. 1986; 27: 3173
• 5c Bégué J.-P, Bonnet-Delpon D, Rock MH. Tetrahedron Lett. 1995; 36: 5003
• 5d Bégué J.-P, Bonnet-Delpon D, Rock MH. J. Chem. Soc., Perkin Trans. 1 1996; 1409
• 5e Ichikawa J, Fukui H, Ishibashi Y. J. Org. Chem. 2003; 68: 7800
• 5f Ichikawa J, Ishibashi Y, Fukui H. Tetrahedron Lett. 2003; 44: 707
• 5g Ichikawa J, Mori T, Iwai Y. Chem. Lett. 2004; 33: 1354
• 5h Miura T, Ito Y, Murakami M. Chem. Lett. 2008; 37: 1006
• 5i Ichikawa J, Iwai Y, Nadano R, Mori T, Ikeda M. Chem. Asian J. 2008; 3: 393
• 5j Fuchibe K, Takahashi M, Ichikawa J. Angew. Chem. Int. Ed. 2012; 51: 12059
• 5k Cai Y, Zeng H, Zhu C, Liu C, Jiang H. Org. Chem. Front. 2020; 7: 1260
• 5l Xiao T, Li L, Zhou L. J. Org. Chem. 2016; 81: 7908
• 5m Lang S, Wiles RJ, Kelly CB, Molander GA. Angew. Chem. Int. Ed. 2017; 56: 15073
• 5n Xia P.-J, Ye Z.-P, Hu Y.-Z, Song D, Xiang H.-Y, Chen X.-Q, Yang H. Org. Lett. 2019; 21: 2658
• 5o He Y, Anand D, Sun Z, Zhou L. Org. Lett. 2019; 21: 3769
• 5p Wiles RJ, Phelan JP, Molander JA. Chem. Commun. 2019; 55: 7599
• 5q Guo Y.-Q, Wang R, Song H, Liu Y, Wang Q. Org. Lett. 2020; 22: 709
• 5r Anand D, Sun Z, Zhou L. Org. Lett. 2020; 22: 2371
• 5s Ichitsuka T, Fujita T, Ichikawa J. ACS Catal. 2015; 5: 5947
• 5t Hayashi T, Huang YH. J. Am. Chem. Soc. 2016; 138: 12340
• 5u Liu Y, Zhou Y, Zhao Y, Qu J. Org. Lett. 2017; 19: 946
• 5v Dai W, Lin Y, Wan Y, Cao S. Org. Chem. Front. 2018; 5: 55
• 5w Wu X, Xie F, Gridnev ID, Zhang W. Org. Lett. 2018; 20: 1638
• 5x Wang P, Pu X, Zhao Y, Wang P, Li Z, Zhu C, Shi Z. J. Am. Chem. Soc. 2018; 140: 9061
• 5y Chen F, Xu X, He Y, Huang G, Zhu S. Angew. Chem. Int. Ed. 2020; 59: 5398
• 5z Yao C, Wang S, Norton J, Hammond M. J. Am. Chem. Soc. 2020; 142: 4793
• 6 For a review on the applications of α-trifluoromethyl alkenes in organic synthesis, see: Tian F, Yan G, Yu J. Chem. Commun. 2019; 55: 13486

For reviews on C–F bond cleavage, see:
• 7a Burdeniuc J, Jedicka B, Crabtree RH. Chem. Ber. 1997; 130: 145
• 7b Amii H, Uneyama K. Chem. Rev. 2009; 109: 2119
• 7c Ahrens T, Kohlmann J, Ahrens M, Braun TF. Chem. Rev. 2015; 115: 931
• 7d Shen Q, Huang Y.-G, Liu C, Xiao J.-C, Chen Q.-Y, Guo Y. J. Fluorine Chem. 2015; 179: 14
• 7e Fujita T, Fuchibe K, Ichikawa J. Angew. Chem. Int. Ed. 2019; 58: 390

For reviews on reductive cross-couplings, see:
• 8a Everson DA, Weix DJ. J. Org. Chem. 2014; 79: 4793
• 8b Moragas T, Correa A, Martin R. Chem. Eur. J. 2014; 20: 8242
• 8c Gu J, Wang X, Xue W, Gong H. Org. Chem. Front. 2015; 2: 1411
• 8d Weix DJ. Acc. Chem. Res. 2015; 48: 1767
• 8e Wang X, Dai Y, Gong H. Top. Curr. Chem. 2016; 374: 43
• 8f Richmond E, Moran JR. Synthesis 2018; 50: 499
• 9a Ichikawa J, Nadano R, Ito N. Chem. Commun. 2006; 4425
• 9b Lan Y, Yang F, Wang C. ACS Catal. 2018; 8: 9245
• 9c Ding D, Lan Y, Lin Z, Wang C. Org. Lett. 2019; 21: 2723
• 9d Lin Z, Lan Y, Wang C. Org. Lett. 2019; 21: 8316
• 9e Lin Z, Lan Y, Wang C. ACS Catal. 2019; 9: 775
• 9f Lu X, Wang X.-X, Gong T.-J, Pi J.-J, He S.-J, Fu Y. Chem. Sci. 2019; 10: 809
• 9g Li J, Rao W, Wang S.-Y, Ji S.-J. J. Org. Chem. 2019; 84: 11542
• 9h Lin Z, Lan Y, Wang C. Org. Lett. 2020; 22: 3509
• 10 While this manuscript was under preparation, Lu et al. reported a related reductive cross-coupling of α-trifluoromethyl alkenes with epoxides, see: Lu X.-Y, Jiang R.-C, Li J.-M, Liu C.-C, Wang Q.-Q, Zhou H.-P. Org. Biomol. Chem. 2020; 18: 3674
• 11 4-Aryl-5,5-difluoropent-4-en-1-ols (3aa–la, 3ab–am); General Procedure A Schlenk tube equipped with a stirrer bar was charged with NiI₂ (8.8 mg, 0.04 mmol, 10 mol %), NaI (30 mg, 0.2 mmol, 0.5 equiv), and Zn (78 mg, 1.2 mmol, 3 equiv). The tube was then evacuated and filled with N₂ (three cycles). DMA (1.0 mL) was added under N₂, followed by the appropriate trifluoromethyl alkene 1 (0.4 mmol, 1.0 equiv) and epoxide 2 (0.8 mmol, 2.0 equiv). The mixture was stirred at rt for 24 h, and then the reaction was quenched by addition of H₂O. The aqueous phase was extracted with EtOAc (3 × 20 mL) and the combined organic phases were washed with brine, dried (Na₂SO₄), filtered, and concentrated in vacuo. The crude material was purified by column chromatography (silica gel, PE–EtOAc). 7,7-Difluoro-1,6-bis(4-methoxyphenyl)-3-methylhept-6-en-3-ol (3aa) Colorless oil; yield: 126 mg (84%). ¹H NMR (400 MHz, CDCl₃): δ = 7.24 (d, J = 7.9 Hz, 2 H), 7.08 (d, J = 8.6 Hz, 2 H), 6.89 (d, J = 8.8 Hz, 2 H), 6.82 (d, J = 8.6 Hz, 2 H), 3.80 (s, 3 H), 3.77 (s, 3 H), 2.60–2.53 (m, 2 H), 2.49–2.42 (m, 2 H), 1.77–1.68 (m, 2 H), 1.59–1.53 (m, 2 H), 1.23 (s, 3 H). ¹³C NMR (101 MHz, CDCl₃): δ = 158.7, 157.8, 153.2 (dd, J = 289.1, 286.2 Hz), 134.3, 129.3 (t, J = 3.4 Hz, 2 C), 129.2 (2 C), 125.7 (t, J = 2.8 Hz), 114.0 (2 C), 113.9 (2 C), 91.9 (dd, J = 20.6, 14.3 Hz), 72.4, 55.3 (2 C), 43.9, 39.9 (t, J = 2.3 Hz), 29.4, 26.7, 22.5. ¹⁹F NMR (376 MHz, CDCl₃): δ = –92.39 (d, J = 46.6 Hz, 1 F), –92.58 (d, J = 46.7 Hz, 1 F). HRMS (ESI): m/z [M + Na]⁺ calcd for C₂₂H₂₆F₂NaO₃: 399.1742; found: 399.1741.