Nickel-Catalyzed α-1,3-Dienylation of 1,3-Dicarbonyl Compounds with Propargylic Carbonates

Abstract

Herein reported is a nickel-catalyzed α-1,3-dienylation reaction of 1,3-dicarbonyl compounds with substituted propargylic (e.g., but-2-ynyl) carbonates. The propargyl unit changes into a 1,3-dienyl unit, which is incorporated at the α-position of the 1,3-dicarbonyl compounds.

Key words

nickel - 1,3-diene - malonate - propargylic carbonate - C–C bond formation

Publication History

Received: 15 September 2020

Accepted after revision: 05 October 2020

Accepted Manuscript online:
05 October 2020

Article published online:
02 November 2020

• References and Notes

• 1a The Chemistry of Dienes and Polyenes, Vol. 1. Rappoport Z. Wiley; Chichester: 1997
• 1b The Chemistry of Dienes and Polyenes, Vol. 2. Rappoport Z. Wiley; Chichester: 2000
• 1c Corey EJ. Angew. Chem. Int. Ed. 2002; 41: 1650
• 1d Nicolaou KC, Snyder SA, Montagnon T, Vassilikogiannakis G. Angew. Chem. Int. Ed. 2002; 41: 1668
• 1e Xiong Y, Sun Y, Zhang G. Tetrahedron Lett. 2018; 59: 347
• 1f Holmes M, Schwartz LA, Krische MJ. Chem. Rev. 2018; 118: 6026
• 2 Locascio TM, Tunge JA. Chem. Eur. J. 2016; 22: 18140
• 3 Ishida N, Hori Y, Okumura S, Murakami M. J. Am. Chem. Soc. 2019; 141: 84
• 4 O’Broin CQ, Guiry PJ. Org. Lett. 2020; 22: 879

For palladium-catalyzed intramolecular reactions, see:
• 5a Fournier-Nguefack C, Lhoste P, Sinou D. Synlett 1996; 553
• 5b Kozawa Y, Mori M. J. Org. Chem. 2003; 68: 8068
• 5c Ambrogio I, Cacchi S, Fabrizi G, Prastaro A. Tetrahedron 2009; 65: 8916
• 5d Nemoto T, Zhao Z, Yokosaka T, Suzuki Y, Wu R, Hamada Y. Angew. Chem. Int. Ed. 2013; 52: 2217
• 5e Daniels DS. B, Jones AS, Thompson AL, Paton R, Anderson A. Angew. Chem. Int. Ed. 2014; 53: 1915
• 5f Ogiwara Y, Sato K, Sakai N. Org. Lett. 2017; 19: 5296

Reviews on transition-metal-catalyzed reactions of propargylic electrophiles:
• 6a Tsuji J, Mandai T. Angew. Chem. Int. Ed. 1996; 34: 2589
• 6b Ma S. Eur. J. Org. Chem. 2004; 1175
• 6c Guo L.-N, Duan X.-H, Liang Y.-M. Acc. Chem. Res. 2011; 44: 111
• 6d Yoshida M. Heterocycles 2013; 87: 1835
• 6e Franckevičius V. Tetrahedron Lett. 2016; 57: 3586
• 6f Roy R, Saha S. RSC Adv. 2018; 8: 31129
• 6g O’Broin CQ, Guiry P. J. Org. Chem. 2020; 85: 10321

Selected examples:
• 7a Behenna DC, Mohr JT, Sherden NH, Marinescu SC, Harned AM, Tani K, Seto M, Ma S, Novák Z, Krout MR, McFadden RM, Roizen JL, Enquist JA, White DE, Levine SR, Petrova KV, Iwashita A, Virgil SC, Stoltz BM. Chem. Eur. J. 2011; 17: 14199
• 7b Ambrogio I, Cacchi S, Fabrizi G, Goggiamani A, Lazzetti A. Eur. J. Org. Chem. 2015; 3147
• 7c Oelke AJ, Sun J, Fu GC. J. Am. Chem. Soc. 2012; 134: 2966
• 7d Watanabe K, Miyazaki Y, Okubo M, Zhou B, Tsuji H, Kawatsura M. Org. Lett. 2018; 20: 5448
• 7e Tang S, Wei W, Yin D, Poznik M, Chruma JJ. Eur. J. Org. Chem. 2019; 3964
• 7f O’Broin CQ, Guiry PJ. Org. Lett. 2019; 21: 5402

Selected examples:
• 8a Jeffery-Luong T, Linstrumelle G. Tetrahedron Lett. 1980; 21: 5019
• 8b Ruitenberg K, Kleijn H, Elsevier CJ, Meijer J, Vermeer P. Tetrahedron Lett. 1981; 22: 1451
• 8c Keinan E, Bosch E. J. Org. Chem. 1986; 51: 4006
• 8d Moriya T, Miyaura N, Suzuki A. Synlett 1994; 149
• 8e Kimura M, Wakamiya Y, Horino Y, Tamaru Y. Tetrahedron Lett. 1997; 38: 3963
• 8f Kalek M, Jahansson T, Jezowska M, Stawinski J. Org. Lett. 2010; 12: 4702
• 8g Molander GA, Sommers EM, Baker SR. J. Org. Chem. 2006; 71: 1563
• 8h Yoshida M, Ohno S, Namba K. Angew. Chem. Int. Ed. 2013; 52: 13597
• 8i Smith MK, Tunge JA. Org. Lett. 2017; 19: 5497
• 8j Wang H, Luo H, Zhang Z, Zheng W.-F, Yin Y, Qian H, Zhang J, Ma S. J. Am. Chem. Soc. 2020; 142: 9763

Selected examples:
• 9a Tsuji J, Watanabe H, Minami I, Shimizu I. J. Am. Chem. Soc. 1985; 107: 2196
• 9b Yoshida M, Fujita M, Ishii T, Ihara M. J. Am. Chem. Soc. 2003; 125: 4874
• 9c Labrosse J.-R, Lhoste P, Delbecq F, Sinou D. Eur. J. Org. Chem. 2003; 2813
• 9d Ambrogio I, Cacchi S, Fabrizi G. Org. Lett. 2006; 8: 2083
• 9e Guo L.-N, Duan X.-H, Bi H.-P, Liu X.-Y, Liang Y.-M. J. Org. Chem. 2007; 72: 1538
• 9f Inuki S, Yoshimitsu Y, Oishi S, Fujii N, Ohno H. J. Org. Chem. 2010; 75: 3831
• 9g Nishioka N, Koizumi T. J. Polym. Sci., Part A: Polym. Chem. 2011; 49: 642
• 9h Schröder SP, Taylor NJ, Jackson P, Franckevičius V. Org. Lett. 2013; 15: 3778
• 9i Nibbs AE, Montgomery TD, Zhu Y, Rawal VH. J. Org. Chem. 2015; 80: 4928
• 9j Wu T, Chen M, Yang Y. J. Org. Chem. 2017; 82: 11304
• 9k Kawase A, Omura H, Doi T, Tsukamoto H. Chem. Lett. 2019; 48: 1402
• 9l Ding L, Gao RD, You S.-L. Chem. Eur. J. 2019; 25: 4330

Selected examples of π-propargyl complexes:
• 10a Gotzig J, Otto H, Werner H. J. Organomet. Chem. 1985; 287: 247
• 10b Jia G, Rheingold AL, Meek DW. Organometallics 1989; 8: 1378
• 10c Wakatsuki Y, Yamazaki H, Maruyama Y, Shimizu I. J. Chem. Soc., Chem. Commun. 1991; 261
• 10d Krivykh VV, Taits ES, Petrovskii PV, Struchkov YT, Yanovskii AI. Mendeleev Commun. 1991; 1: 103
• 10e Huang T.-M, Chen J.-T, Lee G.-H, Wang YA. J. Am. Chem. Soc. 1993; 115: 1170
• 10f Blosser PW, Gallucci JC, Wojcicki A. J. Am. Chem. Soc. 1993; 115: 2994
• 10g Stang PJ, Crittell CM, Arif AM. Organometallics 1993; 12: 4799
• 10h Casey CP, Nash JR, Yi CS, Selmeczy AD, Chung S, Powell DR, Hayashi RK. J. Am. Chem. Soc. 1998; 120: 722
• 10i Cheng Y.-C, Chen Y.-K, Huang T.-M, Yu C.-I, Lee G.-H, Wang Y, Chen J.-T. Organometallics 1998; 17: 2953
• 10j Norambuena VF. Q, Heeres A, Heeres HJ, Meetsma A, Teuben JH, Hessen B. Organometallics 2008; 27: 5672
• 10k Nagae H, Kundu A, Tsurugi H, Mashima K. Organometallics 2017; 36: 3061

For the central attack by nucleophile, see:
• 11a Chen J.-T. Coord. Chem. Rev. 1999; 190-192: 1143
• 11b Su C.-C, Chen J.-T, Lee G.-H, Wang Y. J. Am. Chem. Soc. 1994; 116: 4999
• 11c Tsai F.-Y, Hsu R.-H, Huang T.-M, Chen J.-T, Lee G.-H, Wang Y. J. Organomet. Chem. 1996; 520: 85
• 12 For the formation of π-allylmetals from π-propargylmetals, see ref. 10h,i and 11.
• 13 For a relevant deprotonation reaction of a π-allylpalladium species, see: Takacs JM, Lawson EC, Clement F. J. Am. Chem. Soc. 1997; 119: 5956
• 14 α-Dienylation of Malonate 1 with 2: Typical Procedure Ni(cod)₂ (5.5 mg, 0.020 mmol, 5 mol%) and ligand 5 (15.6 mg, 0.030 mmol, 8 mol%) were placed in a vial. Acetonitrile (2 mL) was added, and the mixture was stirred at room temperature for 5 min. Then, malonate 1 (69.7 mg, 0.40 mmol) and propargyl carbonate 2 (88.5 mg, 0.52 mmol, 1.3 equiv) were added to the mixture, which was stirred at 80 °C for 24 h. After cooled to room temperature, the reaction mixture was passed through a pad of silica gel, which was eluted with ethyl acetate. The filtrate was evaporated to dryness under reduced pressure. The residue was purified by preparative thin-layer chromatography (PTLC; eluent: hexane/ethyl acetate = 10:1) to give a colorless oil (80.4 mg), which was estimated by ¹H NMR spectroscopy to contain 3 (0.33 mmol, 81%) and 4 (0.029 mmol, 7%). ¹H NMR (400 MHz, CDCl₃): δ = 1.26 (t, J = 7.0 Hz, 6 H), 1.63 (s, 3 H), 4.22 (q, J = 7.2 Hz, 4 H), 5.02 (s, 1 H), 5.09 (d, J = 10.8 Hz, 1 H), 5.38 (d, J = 17.2 Hz, 1 H), 5.42 (s, 1 H), 6.31 (dd, J = 17.2, 11.2 Hz, 1 H). ¹³C NMR (101 MHz, CDCl₃): δ = 14.1, 21.2, 58.9, 61.7, 114.1, 115.8, 136.2, 145.2, 171.1. HRMS (APCI⁺): m/z calcd for C₁₂H₁₉O₄ [M + H]⁺: 227.1283; found: 227.1279. IR (ATR): 2983, 1728, 1248, 1219, 1101, 1018 cm^–1.