Rhodium(I)-Catalyzed CO-Gas-Free Arylative Dual-Carbonylation of Alkynes with Arylboronic Acids via the Formyl C–H Activation of Formaldehyde

Abstract

The rhodium(I)-catalyzed reaction of alkynes with aryl­boronic acids in the presence of formaldehyde results in a CO-gas-free arylative dual-carbonylation to produce γ-butenolide derivatives. The simultaneous loading of phosphine-ligated and phosphine-free rhodium(I) complexes is required for efficient catalysis. The former complex catalyzes the abstraction of a carbonyl moiety from formaldehyde through the activation of its formyl C–H bond (decarbonylation) and the latter catalyzes the subsequent dual-incorporation of the resulting carbonyl unit (carbonylation). The use of larger amounts of the phosphine-ligated rhodium(I) complex generates more carbonyl units, leading to the formation γ-butenolides via the dual-incorporation of the carbonyl unit.

Key words

C–H activation - decarbonylation - rhodium - formaldehyde - γ-butenolides - alkynes - arylboronic acids

Publication History

Received: 12 March 2021

Accepted after revision: 29 March 2021

Accepted Manuscript online:
29 March 2021

Article published online:
22 April 2021

• References


For recent reviews on hydroacylation, see:
• 1a Willis MC. Chem. Rev. 2010; 110: 725
• 1b Leung JC, Krische MJ. Chem. Sci. 2012; 3: 2202
• 1c Yang L, Huang H. Catal. Sci. Technol. 2012; 2: 1099
• 2a First report, stoichiometric reaction, Rh: Tsuji J, Ohno K. Tetrahedron Lett. 1965; 3969

For catalytic Rh reactions, see:
• 2b Doughty DH, Pignolet LH. J. Am. Chem. Soc. 1978; 100: 7083
• 2c Kreis M, Palmelund A, Bunch L, Madsen R. Adv. Synth. Catal. 2006; 348: 2148
• 2d Fessard TC, Andrews SP, Motoyoshi H, Carreira EM. Angew. Chem. Int. Ed. 2007; 46: 9331
• 2e Fristrup P, Kreis M, Palmelund A, Norrby P.-O, Madsen R. J. Am. Chem. Soc. 2008; 130: 5206
• 2f Catalytic, Ir: Iwai T, Fujihara T, Tsuji Y. Chem. Commun. 2008; 6215
• 2g Catalytic, Pd: Modak A, Deb A, Patra T, Rana T, Maity S, Maiti D. Chem. Commun. 2012; 48: 4253
• 3 For a selected paper on the utilization of the decarbonylation in a total synthesis, see: Zhang H, Padwa A. Tetrahedron Lett. 2006; 47: 3905

For reviews on the CO-gas-free carbonylation reaction including the use of aldehydes as a carbonyl source, see:
• 4a Morimoto T, Kakiuchi K. Angew. Chem. Int. Ed. 2004; 43: 5580
• 4b Wu L, Liu Q, Jackstell R, Beller M. Angew. Chem. Int. Ed. 2014; 53: 6310
• 4c Gautam P, Bhanage BM. Catal. Sci. Technol. 2015; 5: 4663
• 4d Cao J, Zheng Z.-J, Xu Z, Xu LW. Coord. Chem. Rev. 2017; 336: 43
• 4e Gorbunov DN, Nenasheva MV, Kardasheva YS, Karakhanov EA. Russ. Chem. Bull. 2020; 69: 625
• 5 Morimoto T, Fuji K, Tsutsumi K, Kakiuchi K. J. Am. Chem. Soc. 2002; 124: 3806
• 6a Morimoto T, Yamazaki K, Hirano A, Tsutsumi K, Kagawa N, Kakiuchi K, Harada Y, Fukumoto Y, Chatani N, Nishioka T. Org. Lett. 2009; 11: 1777
• 6b Makado G, Morimoto T, Sugimoto Y, Tsutsumi K, Kagawa N, Kakiuchi K. Adv. Synth. Catal. 2010; 352: 299
• 6c Wang C, Morimoto T, Kaneshiro H, Tanimoto H, Nishiyama Y, Kakiuchi K, Artok L. Synlett 2014; 25: 1155
• 6d Furusawa T, Morimoto T, Ikeda K, Tanimoto H, Nishiyama Y, Kakiuchi K, Jeong N. Tetrahedron 2015; 71: 875
• 6e Furusawa T, Morimoto T, Nishiyama Y, Tanimoto H, Kakiuchi K. Chem. Asian J. 2016; 11: 2312
• 6f Furusawa T, Tanimoto H, Nishiyama Y, Morimoto T, Kakiuchi K. Adv. Synth. Catal. 2017; 359: 240
• 6g Furusawa T, Tanimoto H, Nishiyama Y, Morimoto T, Kakiuchi K. Chem. Lett. 2017; 46: 926
• 6h Pan J, Morimoto T, Kobayashi H, Tanimoto H, Kakiuchi K. Heterocycles 2019; 98: 519
• 6i Morimoto T, Yamashita M, Tomiie A, Tanimoto H, Kakiuchi K. Chem. Asian J. 2020; 15: 473

For books on rhodium-catalyzed reactions in organic synthesis, see:
• 7a Modern Rhodium-Catalyzed Organic Reactions . Evans PA. Wiley-VCH; Weinheim: 2005
• 7b Rhodium Catalysis in Organic Synthesis . Tanaka K. Wiley-VCH; Weinheim: 2019
• 8a Laduwahetty T. Contemp. Org. Synth. 1995; 2: 133
• 8b Collins I. Contemp. Org. Synth. 1996; 3: 295
• 8c Collins I. Contemp. Org. Synth. 1997; 4: 281
• 9 Abbreviations: cod = 1,5-cyclooctadiene, dppp = 1,3-bis(diphenylphosphino)propane, BIPHEP = 2,2′-bis(diphenylphosphino)biphenyl, BINAP = 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl, dppf = 1,1′-ferrocenediyl-bis(diphenylphosphine), dppb = 1,3-bis(diphenylphosphino)butane.
• 10a Aksin Ö, Dege N, Artok L, Türkmen H, Çetinkaya B. Chem. Commun. 2006; 3187
• 10b Kuş M, Aksin Ö, Ziyanak F, Artok L. Synlett 2008; 2587
• 10c Artok L, Kuş M, Aksin-Artok Ö, Dege NF, Özkilinç FY. Tetrahedron 2009; 65: 9125
• 11 Bunten KA, Farrar DH, Poë AJ, Lough A. Organometallics 2002; 21: 3344
• 12 James BR, Mahajan D. Can. J. Chem. 1977; 57: 180
• 13 [RhCl(C₂H₄)₂]₂ instead of [RhCl(cod)]₂ also catalyzed the reaction of 1 with 2a in the presence of formaldehyde under the above standard conditions to give 3a and 4a in 64% yield (3a, 11%; 4a, 53%) along with 5a in 6% yield.
• 14 The ³¹P NMR spectrum shows that some signals for small amounts of P are also observed in the area of 20–30 ppm, which are split by coupling with a rhodium nucleus. Thus, other dppp-ligated rhodium(I) species are also present in the mixture.

For RhCl(dppp)₂, see:
• 15a Shibata T, Toshida N, Takagi K. Org. Lett. 2002; 4: 1619
• 15b Shibata T, Toshida N, Takagi K. J. Org. Chem. 2002; 67: 7446
• 15c For [RhCl(dppp)]₂, see reference 2e.
• 16 For a representative review on vinylogous aldol reactions, see: Casiraghi G, Zanardi F, Appendino G, Rassu G. Chem. Rev. 2000; 100: 1929
• 17 Giordano G, Crabtree RH. Inorg. Synth. 1979; 19: 218