Tandem Nickel-Catalyzed Dimerization/(4+2) Cycloaddition of Terminal Alkynes with Four-Membered Ring Ketones

Abstract

Controlling the behavior of terminal alkynes in metal-catalyzed intermolecular tandem reactions is a formidable challenge despite the potential advantage offered by these strategies in modern synthesis. Herein, we describe that a nickel catalyst enables a tandem process involving the rapid dimerization of terminal alkynes into 1,3-enynes and the cycloaddition of these intermediates with an azetidinone, an oxetanone or benzocyclobutenones. Significantly, the slow or sequential addition of reagents and catalysts is not required to orchestrate their reactivity. These results are in stark contrast with previous cycloadditions of terminal alkynes with strained four-membered ring substrates, which previously led to oligomerization or cyclotrimerization, except in the case of tert-butylacetylene.

Key words

carbon–carbon bond activation - nickel - catalysis - azetidinone - oxetanone - benzocyclobutenones - tandem

Publication History

Received: 20 September 2021

Accepted after revision: 18 October 2021

Accepted Manuscript online:
18 October 2021

Article published online:
22 November 2021

• References


For general reviews, see:
• 1a Multicomponent Reactions . Zhu J, Bienaymé H. Wiley-VCH; Weinheim: 2005
• 1b Brauch S, van Berkel SS, Westermann B. Chem. Soc. Rev. 2013; 42: 4948
• 2a Hoberg H, Oster BW. Synthesis 1982; 324
• 2b Hong P, Yamazaki H. Tetrahedron Lett. 1977; 18: 1333
• 2c Doyle MP, Shanklin MS. Organometallics 1994; 13: 1081
• 2d Costa M, Dias FS, Chiusoli GP, Gazzola GL. J. Organomet. Chem. 1995; 488: 47
• 2e Tanaka K, Suzuki N, Nishida G. Eur. J. Org. Chem. 2006; 3917
• 2f Zhao L, de Meijere A. Adv. Synth. Catal. 2006; 348: 2484
• 2g Oberg KM, Lee EE, Rovis T. Tetrahedron 2009; 65: 5056
• 2h Liu Y, Yan X, Yang N, Xi C. Catal. Commun. 2011; 12: 489
• 2i Zhong Y, Spahn NA, Stolley RM, Nguyen H, Louie J. Synlett 2015; 26: 307

Selected examples:
• 3a Chalk AJ. J. Am. Chem. Soc. 1972; 94: 5928
• 3b Huang D.-J, Sambaiah T, Cheng C.-H. New J. Chem. 1998; 1147
• 3c Sambaiah T, Huang D.-J, Cheng C.-H. J. Chem. Soc., Perkin Trans. 1 2000; 195
• 3d Ikeda S.-i, Mori N, Sato Y. J. Am. Chem. Soc. 1997; 119: 4779
• 3e Mori N, Ikeda S.-i, Sato Y. J. Am. Chem. Soc. 1999; 121: 2722
• 3f Ikeda S.-i, Kondo H, Mori N. Chem. Commun. 2000; 815
• 3g Takeuchi R, Nakaya Y. Org. Lett. 2003; 5: 3659
• 3h Hilt G, Hess W, Vogler T, Hengst C. J. Organomet. Chem. 2005; 690: 5170
• 3i Ogoshi S, Ikeda H, Kurosawa H. Angew. Chem. Int. Ed. 2007; 46: 4930
• 3j Tanaka K, Takahashi Y, Suda T, Hirano M. Synlett 2008; 1724
• 3k Lane TK, D’Souza BR, Louie J. J. Org. Chem. 2012; 77: 7555
• 3l Wang C, Wang D, Xu F, Pan B, Wan B. J. Org. Chem. 2013; 78: 3065
• 3m Mori T, Akioka Y, Kawahara H, Ninokata R, Onodera G, Kimura M. Angew. Chem. Int. Ed. 2014; 53: 10434
• 4a Saito S, Masuda M, Komagawa S. J. Am. Chem. Soc. 2004; 126: 10540
• 4b Komagawa S, Saito S. Angew. Chem. Int. Ed. 2006; 45: 2446
• 4c Komagawa S, Takeuchi K, Sotome I, Azumaya I, Masu H, Yamasaki R, Saito S. J. Org. Chem. 2009; 74: 3323

For selected recent reviews on metal-catalyzed C–C bond activation, see:
• 5a Souillart L, Cramer N. Chem. Rev. 2015; 115: 9410
• 5b Fumagalli G, Stanton S, Bower JF. Chem. Rev. 2017; 117: 9404
• 5c Deng L, Dong G. Trends Chem. 2020; 2: 183
• 5d Murakami M, Ishida N. Chem. Rev. 2021; 121: 264
• 6 Murakami M, Ashida S, Matsuda T. J. Am. Chem. Soc. 2005; 127: 6932
• 7a Huffman MA, Liebeskind LS. J. Am. Chem. Soc. 1991; 113: 2771
• 7b Auvinet AL, Harrity JP. Angew. Chem. Int. Ed. 2011; 50: 2769
• 7c Stalling T, Harker WR. R, Auvinet AL, Cornell EJ, Harrity JP. Chem. Eur. J. 2015; 21: 2701
• 8a Juliá-Hernández F, Ziadi A, Nishimura A, Martin R. Angew. Chem. Int. Ed. 2015; 54: 9537

For other selected leading examples of intramolecular cycloadditions of alkenes, alkynes, and 1,3-dienes with other metal catalysts, see:
• 8b Xu T, Dong G. Angew. Chem. Int. Ed. 2012; 51: 7567
• 8c Chen P.-H, Xu T, Dong G. Angew. Chem. Int. Ed. 2014; 53: 1674
• 8d Lu G, Fang C, Xu T, Dong G, Liu P. J. Am. Chem. Soc. 2015; 137: 8274
• 8e Zhang J, Wang X, Xu T. Nat. Commun. 2021; 12: 3022
• 9a Ho KY. T, Aïssa C. Chem. Eur. J. 2012; 18: 3486
• 9b Kumar P, Louie J. Org. Lett. 2012; 14: 2026
• 9c Ishida N, Yuhki T, Murakami M. Org. Lett. 2012; 14: 3898
• 9d Thakur A, Evangelista JL, Kumar P, Louie J. J. Org. Chem. 2015; 80: 9951
• 9e Barday M, Ho KY. T, Halsall CT, Aïssa C. Org. Lett. 2016; 18: 1756
• 9f Barday M, Janot C, Clare D, Carr-Knox C, Higginson B, Aïssa C. Synthesis 2017; 49: 3582
• 9g Elwrfalli F, Esvan YJ, Robertson CM, Aïssa C. Chem. Commun. 2019; 55: 497
• 10 For a recent review, see: Trost BM, Masters JT. Chem. Soc. Rev. 2016; 45: 2212
• 11 Ogoshi S, Ueta M, Oka M.-a, Kurosawa H. Chem. Commun. 2004; 2732
• 12 Signals indicative of decomposition appeared in the ¹³C NMR spectrum during the long acquisition required to see the broad signals that are characteristic of 3af.
• 13a Moser WH, Sun L, Huffman JC. Org. Lett. 2001; 3: 3389
• 13b Eastham SA, Ingham SP, Hallett MR, Herbert J, Quayle P, Raftery J. Tetrahedron Lett. 2006; 47: 2299
• 14 Benzocyclobutenones that possess substituents on the four-membered ring but not on the aromatic ring failed to undergo the tandem reaction depicted in Scheme 6.
• 15 Guo J.-H, Liu Y, Lin X.-X, Tang T.-M, Wang B.-Q, Hu P, Zhao K.-Q, Song F, Shi Z.-H. Angew. Chem. Int. Ed. 2021; 60: 19079
• 16 After five minutes of reaction, alkyne/1,3-enyne = 1:1.4 by method C; alkyne/1,3-enyne = 1:1.8 by method D.
• 17 Maciejewski H, Sydor A, Marciniec B, Kubicki M, Hitchcock PB, Wawrzyńczak A, Dutkiewicz M, Fiedorow R, Szubert K, Kurdykowska M, Celka L. Inorg. Chim. Acta 2006; 359: 2989
• 18 Mynott R, Mollbach A, Wilke G. J. Organomet. Chem. 1980; 199: 107
• 19 Ligand exchange of PtBu₃ from [Ni(PtBu₃)₂] is sufficiently slow that separate resonances for this complex and the free ligand can be observed at room temperature at 97.1 ppm and 62.3 ppm, respectively.
• 20 Tolman CA. J. Am. Chem. Soc. 1970; 92: 2956
• 21 Huang C, He R, Shen W, Li M. J. Mol. Model. 2015; 21: 135
• 22a Li Y, Lin Z. Organometallics 2013; 32: 3003
• 22b A mono-phosphine complex might be preferred in the case of benzocyclobutenones (see reference 15).
• 23 Steves JA, Preger Y, Martinelli JR, Welch CJ, Root TW, Hawkins JM, Stahl SS. Org. Process Res. Dev. 2015; 19: 1548
• 24 Fandrick DR, Reeves JT, Tan Z, Lee H, Song JJ, Yee NK, Senanayake CH. Org. Lett. 2009; 11: 5458
• 25 Denmark SE, Tymonko SA. J. Am. Chem. Soc. 2005; 127: 8004
• 26 Chen P.-H, Savage NA, Dong G. Tetrahedron 2014; 70: 4135
• 27 Qin Y, Zhan J.-L, Shan T.-t, Xu T. Tetrahedron Lett. 2019; 60: 925