Nickel-Catalyzed Hydroalkynylation of 1,3-Dienes with Simple Alkynes

Abstract

A hydroalkynylation reaction of 1,3-dienes with simple alkynes, facilitated by an efficient nickel catalyst system with the 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene (Xantphos) ligand, is presented. This reaction displays a broad substrate range for alkynes, encompassing both aryl alkynes and alkyl alkynes, thereby overcoming previous constraints in 1,3-diene hydroalkynylation. The method offers a convenient and direct means for obtaining allylic alkynes with high atom and step economy.

Key words

nickel catalysis - hydroalkynylation - dienes - alkynes - regioselectivity

Publication History

Received: 12 September 2023

Accepted after revision: 16 October 2023

Article published online:
16 November 2023

• References and Notes

• 1a Wang Z.-X, Bai X.-Y, Li B.-J. Synlett 2017; 28: 509
• 1b Wang Y, He Y, Zhu S. Acc. Chem. Res. 2022; 55: 3519
• 1c Zhao W, Lu H.-X, Zhang W.-W, Li B.-J. Acc. Chem. Res. 2023; 56: 308
• 1d Sun X.-Y, Yao B.-Y, Xuan B, Xiao L.-J, Zhou Q.-L. Chem Catal. 2022; 2: 3140
• 2a Matsuyama N, Tsurugi H, Satoh T, Miura M. Adv. Synth. Catal. 2008; 350: 2274
• 2b Sakurada T, Sugiyama Y.-k, Okamoto S. J. Org. Chem. 2013; 78: 3583
• 3a Saito S, Kawasaki T, Tsuboya N, Yamamoto Y. J. Org. Chem. 2001; 66: 796
• 3b Ogata K, Murayama H, Sugasawa J, Suzuki N, Fukuzawa S.-i. J. Am. Chem. Soc. 2009; 131: 3176
• 3c Rodrigo SK, Powell IV, Coleman MG, Krause JA, Guan H. Org. Biomol. Chem. 2013; 11: 7653
• 3d Yang K, Wang P, Sun Z.-Y, Guo M, Zhao W, Tang X, Wang G. Org. Lett. 2021; 23: 3933
• 3e Saito S, Yamamoto Y. Chem. Rev. 2000; 100: 2901
• 4a Yin J, Chisholm JD. Chem. Commun. 2006; 632
• 4b Shirakura M, Suginome M. J. Am. Chem. Soc. 2009; 131: 5060
• 4c Tenaglia A, Le Jeune K, Giordano L, Buono G. Org. Lett. 2011; 13: 636
• 4d Teng H.-L, Ma Y, Zhan G, Nishiura M, Hou Z. ACS Catal. 2018; 8: 4705
• 4e Dian L, Marek I. ACS Catal. 2020; 10: 1289
• 5a Trost BM, Kottirsch G. J. Am. Chem. Soc. 1990; 112: 2816
• 5b Yamaguchi M, Omata K, Hirama M. Tetrahedron Lett. 1994; 35: 5689
• 5c Bruyere D, Grigg R, Hinsley J, Hussain RK, Korn S, De La Cierva CO, Sridharan V, Wang J. Tetrahedron Lett. 2003; 44: 8669
• 5d Rubin M, Markov J, Chuprakov S, Wink DJ, Gevorgyan V. J. Org. Chem. 2003; 68: 6251
• 5e Pradhan TR, Kim HW, Park JK. Angew. Chem. Int. Ed. 2018; 57: 9930
• 5f Jeanne-Julien L, Masson G, Kouoi R, Regazzetti A, Genta-Jouve G, Gandon V, Roulland E. Org. Lett. 2019; 21: 3136
• 6a Tenaglia A, Giordano L, Buono G. Org. Lett. 2006; 8: 4315
• 6b Fan B.-M, Yang Q.-j, Hu J, Fan C.-l, Li S.-f, Yu L, Huang C, Tsang WW, Kwong FY. Angew. Chem. Int. Ed. 2012; 51: 7821
• 6c Fan B.-M, Xu J, Yang Q, Li S, Chen H, Liu S, Yu L, Zhou Y, Wang L. Org. Lett. 2013; 15: 5956

For selected examples of coordination-assisted hydroalkynylation of alkenes, see:
• 7a Zhang W, Wang Z, Bai X, Li B. Youji Huaxue 2020; 40: 1087
• 7b Bai Z, Bai Z, Song F, Wang H, Chen G, He G. ACS Catal. 2020; 10: 933
• 7c Gao P.-C, Wang Z.-X, Li B.-J. Org. Lett. 2021; 23: 9500
• 7d Bai X.-Y, Zhang W.-W, Li Q, Li B.-J. J. Am. Chem. Soc. 2018; 140: 506
• 8 For hydroalkynylation of vinyl ethers, see: Hosseyni S, Smith CA, Shi X. Org. Lett. 2016; 18: 6336

For selected examples of nucleophilic addition of alkynes to electron-deficient alkenes, see:
• 9a Knöpfel TF, Carreira EM. J. Am. Chem. Soc. 2003; 125: 6054
• 9b Yazaki R, Kumagai N, Shibasaki M. J. Am. Chem. Soc. 2010; 132: 10275
• 9c Sawano T, Ashouri A, Nishimura T, Hayashi T. J. Am. Chem. Soc. 2012; 134: 18936
• 9d Villarino L, García-Fandiño R, López F, Mascareñas JL. Org. Lett. 2012; 14: 2996
• 10a Shirakura M, Suginome M. J. Am. Chem. Soc. 2008; 130: 5410
• 10b Shirakura M, Suginome M. Org. Lett. 2009; 11: 523
• 11 Shirakura M, Suginome M. Angew. Chem. Int. Ed. 2010; 49: 3827
• 12 For related linear dimerizations of terminal acetylenes with 1,3-dienes, see: Mitsudo T, Nakagawa Y, Watanabe K, Hori Y, Misawa H, Watanabe H, Watanabe Y. J. Org. Chem. 1985; 50: 565
• 13a Cheng L, Li M.-M, Xiao L.-J, Xie J.-H, Zhou Q.-L. J. Am. Chem. Soc. 2018; 140: 11627
• 13b Lv X.-Y, Fan C, Xiao L.-J, Xie J.-H, Zhou Q.-L. CCS Chem. 2019; 1: 328
• 13c Cheng L, Li M.-M, Wang B, Xiao L.-J, Xie J.-H, Zhou Q.-L. Chem. Sci. 2019; 10: 10417
• 13d Cheng L, Li M.-M, Li M.-L, Xiao L.-J, Xie J.-H, Zhou Q.-L. CCS Chem. 2022; 4: 2612
• 13e Ma J.-T, Zhang T, Yao B.-Y, Xiao L.-J, Zhou Q.-L. J. Am. Chem. Soc. 2023; 145: 19195
• 13f Xiao L.-J, Ye M.-C, Zhou Q.-L. Synlett 2019; 30: 361
• 14 Zhang A, RajanBabu TV. J. Am. Chem. Soc. 2006; 128: 54
• 15 Bini L, Müller C, Wilting J, von Chrzanowski L, Spek AL, Vogt D. J. Am. Chem. Soc. 2007; 129: 12622
• 16 1,1′-[(1E)-3-Methylpent-1-en-4-yne-1,5-diyl]dibenzene (3a); Typical Procedure: In an N₂-filled glove box, an oven-dried sealed tube equipped with a stirrer bar was charged with Ni(COD)₂ (2.8 mg, 0.01 mmol) and Xantphos (11.6 mg, 0.02 mmol). THF (1 mL) and H₂O (2.0 mmol) were injected into the tube, and the solution was stirred at 25 °C under N₂ for 1 min. (E)-1-Phenyl-1,3-butadiene (1a; 39.0 mg, 0.3 mmol) and phenylacetylene (2a; 10.2 mg, 0.1 mmol) were then successively introduced into the system. The tube was sealed with a Teflon-lined screw cap and removed from the glove box, and the mixture was stirred at 60 °C for 12 h, then cooled to r.t. The resulting mixture was concentrated and the residue was purified by column chromatography (silica gel, pentane) to give a colorless oil; yield: 16.0 mg (0.069 mmol, 69%). ¹H NMR (400 MHz, CDCl₃): δ = 7.50–7.44 (m, 2 H), 7.41 (d, J = 7.2 Hz, 2 H), 7.37–7.28 (m, 5 H), 7.24 (d, J = 7.1 Hz, 1 H), 6.70 (dd, J = 15.7, 1.4 Hz, 1 H), 6.25 (dd, J = 15.7, 6.2 Hz, 1 H), 3.61–3.52 (m, 1 H), 1.46 (d, J = 7.0 Hz, 3 H). ¹³C NMR (101 MHz, CDCl₃): δ = 137.1, 131.6, 131.1, 129.5, 128.5, 128.2, 127.7, 127.3, 126.3, 123.7, 91.6, 82.7, 29.6, 21.7.