Mechanisms for nickel(0)/N-heterocyclic carbene-catalyzed intramolecular alkene hydroacylation: insights from a DFT study

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Abstract

Density functional calculations have been applied to study and elucidate nickel(0)/N-heterocyclic carbene-catalyzed intramolecular alkene hydroacylation. The calculations showed that nickel(0)-catalyzed intramolecular alkene hydroacylation involved four potential reaction channels (I, II, III, and IV), and pathway IV was predicted to be more favorable than the other three. Two pathways, I and II, had three steps (oxidative addition, hydrogen migration, reductive elimination), and the rate-determining step was hydrogen migration. Pathway III proceeded through oxidative cyclization, β-hydride elimination, and hydrogen migration, and the rate-determining step was β-hydride elimination. Pathway IV included four steps (oxidative cyclization, dimerization, β-hydride elimination, hydrogen migration), and the rate-determining step was again β-hydride elimination. Oxidative cyclization was easy and led to rapid dimerization, greatly reducing the free energy of β-hydride elimination. The binuclear nickelacycle intermediate was observed in Ogoshi’s experiments, and it was identified by nuclear magnetic resonance (NMR). The dominant product was the five-membered benzocyclic ketone p1. All results agreed with Ogoshi’s experiments.

Graphical Abstract

Nickel(0)-catalyzed intramolecular alkene hydroacylation involved four potential reaction channels. The binuclear nickelacycle intermediate was important, and the dimerization greatly reduced the free energy of the β-hydride elimination.

Keywords

Nickel N-heterocyclic carbene Hydroacylation Alkene DFT 
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Notes

Acknowledgements

This work was supported by the Natural Science Foundation of China (nos. 31270723, 31370686), the Natural Science Foundation of Shandong Province, China (nos. ZR2013CQ014, ZR2015BM026), and the Youth Foundation of Shandong Agricultural University (no. 23824).

Supplementary material

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References

  1. 1.
    Zhang FL, Hong K, Li TJ, Park H, Yu JQ (2016) Functionalization of C(sp 3)–H bonds using a transient directing group. Science 351:252–256Google Scholar
  2. 2.
    Murphy SK, Park J, Cruz FA, Dong VM (2015) Rh-catalyzed C–C bond cleavage by transfer hydroformylation. Science 347:56–60Google Scholar
  3. 3.
    Quasdorf KW, Overman LE (2014) Catalytic enantioselective synthesis of quaternary carbon stereocentres. Nature 516:181–191CrossRefGoogle Scholar
  4. 4.
    Yang L, Huang H (2015) Transition-metal-catalyzed direct addition of unactivated C–H bonds to polar unsaturated bonds. Chem Rev 115:3468–3517Google Scholar
  5. 5.
    Willis MC (2010) Transition metal catalyzed alkene and alkyne hydroacylation. Chem Rev 110:725–748CrossRefGoogle Scholar
  6. 6.
    Frost BM (2002) On inventing reactions for atom economy. Acc Chem Res 35:695–705CrossRefGoogle Scholar
  7. 7.
    Tsuda T, Kiyoi T, Saegusa T (1990) Nickel(0)-catalyzed hydroacylation of alkynes with aldehydes to α,β-enones. J Org Chem 55:2554–2558Google Scholar
  8. 8.
    Davis JL, Arndtsen BA (2000) Sequential insertion of carbon monoxide and imines into nickel-methyl bonds: a new route to imine hydroacylation. Organometallics 19:4657–4659CrossRefGoogle Scholar
  9. 9.
    Taniguchi H, Ohmura T, Suginome M (2009) Nickel-catalyzed ring-opening hydroacylation of methylenecyclopropanes: synthesis of γ,δ-unsaturated ketones from aldehydes. J Am Chem Soc 131:11298–11299Google Scholar
  10. 10.
    Hoshimoto Y, Hayashi Y, Suzuki H, Ohashi M, Ogoshi S (2012) Synthesis of five- and six-membered benzocyclic ketones through intramolecular alkene hydroacylation catalyzed by nickel(0)/N-heterocyclic carbenes. Angew Chem Int Ed 51:10812–10815Google Scholar
  11. 11.
    Hoshimoto Y, Ohashi M, Ogoshi S (2015) Catalytic transformation of aldehydes with nickel complexes through η2 coordination and oxidative cyclization. Acc Chem Res 48:1746–1755Google Scholar
  12. 12.
    Chen QA, Kim DK, Dong VM (2014) Regioselective hydroacylation of 1,3-dienes by cobalt catalysis. J Am Chem Soc 136:3772–3775CrossRefGoogle Scholar
  13. 13.
    Yang J, Yoshikai N (2014) Cobalt-catalyzed enantioselective intramolecular hydroacylation of ketones and olefins. J Am Chem Soc 136:16748–16751CrossRefGoogle Scholar
  14. 14.
    Yang J, Yoshikai N (2016) Cobalt-catalyzed annulation of salicylaldehydes and alkynes to form chromones and 4-chromanones. Angew Chem Int Ed 55:2870–2874CrossRefGoogle Scholar
  15. 15.
    Chen S, Li X, Zhao H, Li B (2014) CuBr-promoted formal hydroacylation of 1-alkynes with glyoxal derivatives: an unexpected synthesis of 1,2-dicarbonyl-3-enes. J Org Chem 79:4137–4141CrossRefGoogle Scholar
  16. 16.
    Pan JL, Chen T, Zhang ZQ, Li YF, Zhang XM, Zhang FM (2016) A Cu-mediated one-pot Michael addition/α-arylation strategy using a diaryliodonium salt: a direct and efficient approach to α-aryl-β-substituted cyclic ketone scaffolds. Chem Commun 52:2382–2385CrossRefGoogle Scholar
  17. 17.
    Chen Q, Cruz FA, Dong VM (2015) Alkyne hydroacylation: switching regioselectivity by tandem ruthenium catalysis. J Am Chem Soc 137:3157–3160CrossRefGoogle Scholar
  18. 18.
    Miura H, Takeuchi K, Shishido T (2016) Intermolecular [2 + 2 + 1] carbonylative cycloaddition of aldehydes with alkynes, and subsequent oxidation to γ-hydroxybutenolides by a supported ruthenium catalyst. Angew Chem Int Ed 55:278–282CrossRefGoogle Scholar
  19. 19.
    Saxena A, Perez F, Krische MJ (2016) Ruthenium(0)-catalyzed [4 + 2] cycloaddition of acetylenic aldehydes with α-ketols: convergent construction of angucycline ring systems. Angew Chem Int Ed 55:1493–1497Google Scholar
  20. 20.
    Souillart L, Cramer N (2014) Highly enantioselective rhodium(I)-catalyzed carbonyl carboacylations initiated by C–C bond activation. Angew Chem Int Ed 53:9640–9644Google Scholar
  21. 21.
    Johnson KF, Schmidt AC, Stanley LM (2015) Rhodium-catalyzed enantioselective hydroacylation of ortho-allylbenzaldehydes. Org Lett 17:4654–4657Google Scholar
  22. 22.
    Hooper JF, Seo S, Truscott FR, Neuhaus JD, Willis MC (2016) α-Amino aldehydes as readily available chiral aldehydes for Rh-catalyzed alkyne hydroacylation. J Am Chem Soc 138:1630–1634Google Scholar
  23. 23.
    Fujihara T, Tatsumi K, Terao J, Tsujis Y (2013) Palladium-catalyzed formal hydroacylation of allenes employing acid chlorides and hydrosilanes. Org Lett 15:2286–2289CrossRefGoogle Scholar
  24. 24.
    Ai W, Wu Y, Tang H, Yang X, Yang Y, Li Y, Zhou B (2015) Rh(III)- or Ir(III)-catalyzed ynone synthesis from aldehydes via chelation-assisted C–H bond activation. Chem Commun 51:7871–7874Google Scholar
  25. 25.
    Shi S, Wang T, Weingand V, Rudolph M, Hashmi ASK (2014) Gold(I)-catalyzed diastereoselective hydroacylation of terminal alkynes with glyoxals. Angew Chem Int Ed 53:1148–1151CrossRefGoogle Scholar
  26. 26.
    Meng QX, Shen W, He RX, Li M (2011) Theoretical investigation of Ni(PMe3)4-catalyzed intermolecular hydroacylation of alkynes with benzaldehydes. Transition Met Chem 36:793–799Google Scholar
  27. 27.
    Wang F, Zhu SH, Meng QX, Yin HZ (2015) Theoretical studies of nickel-catalyzed ring-opening hydroacylation of methylenecyclopropanes and benzaldehydes. J Mol Model 21:203(1–8)Google Scholar
  28. 28.
    Parr RG, Yang W (1989) Density-functional theory of atoms and molecules. Oxford University Press, New YorkGoogle Scholar
  29. 29.
    Becke AD (1993) Density-functional thermochemistry. III. The role of exact exchange. J Chem Phys 98:5648–5652CrossRefGoogle Scholar
  30. 30.
    Lee C, Yang W, Parr RG (1988) Development of the Colle–Salvetti correlation–energy formula into a functional of the electron density. Phys Rev B 37:785–789Google Scholar
  31. 31.
    Rassolov VA, Ratner MA, Pople JA, Redfern PC, Curtiss LA (2001) 6-31G* basis set for third-row atoms. J Comput Chem 22:976–984CrossRefGoogle Scholar
  32. 32.
    Petersson GA, Bennett A, Tensfeldt TG, Al-Laham MA, Shirley WA, Mantzaris J (1988) A complete basis set model chemistry. I. The total energies of closed-shell atoms and hydrides of the first-row atoms. J Chem Phys 89:2193–2218CrossRefGoogle Scholar
  33. 33.
    Heher WJ, Ditchfield R, Pople JA (1972) Self-consistent molecular orbital methods. 12. Further extensions of Gaussian-type basis sets for use in molecular-orbital studies of organic-molecules. J Chem Phys 56:2257–2261CrossRefGoogle Scholar
  34. 34.
    Hay PJ, Wadt WR (1985) Ab initio effective core potentials for molecular calculations—potentials for the transition-metal atoms Sc to Hg. J Chem Phys 82:270–283Google Scholar
  35. 35.
    Wadt WR, Hay PJ (1985) Ab initio effective core potentials for molecular calculations—potentials for main group elements Na to Bi. J Chem Phys 82:284–298Google Scholar
  36. 36.
    Hay PJ, Wadt WR (1985) Ab initio effective core potentials for molecular calculations—potentials for K to Au including the outermost core orbitals. J Chem Phys 82:299–310Google Scholar
  37. 37.
    Ehlers AW, Böhme M, Dapprich S, Gobbi A, Höllwarth A, Jonas V, Köhler KF, Stegmann R, Veldkamp A, Frenking G (1993) A set of f-polarization functions for pseudo-potential basis sets of the transition metals Sc—Cu, Y—Ag and La—Au. Chem Phys Lett 208:111–114Google Scholar
  38. 38.
    Gonzalez C, Schlegel HB (1990) Reaction path following in mass-weighted internal coordinates. J Phys Chem 94:5523–5527CrossRefGoogle Scholar
  39. 39.
    Carpenter JE, Weinhold F (1988) Analysis of the geometry of the hydroxymethyl radical by the "different hybrids for different spins" natural bond orbital procedure. J Mol Struct (THEOCHEM) 169:41–50CrossRefGoogle Scholar
  40. 40.
    Foster JP, Weinhold F (1980) Natural hybrid orbitals. J Am Chem Soc 102:7211–7218CrossRefGoogle Scholar
  41. 41.
    Reed AE, Weinstock RB, Weinhold F (1985) Natural population analysis. J Chem Phy 83:735–746CrossRefGoogle Scholar
  42. 42.
    Reed AE, Curtiss LA, Weinhold F (1988) Intermolecular interactions from a natural bond orbital, donor–acceptor viewpoint. Chem Rev 88:899–926Google Scholar
  43. 43.
    Glendening ED, Badenhoop JK, Reed AE, Carpenter JE, Bohmann JA, Morales CM, Weinhold F (2001) NBO 5.0. Theoretical Chemistry Institute, University of Wisconsin, MadisonGoogle Scholar
  44. 44.
    Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson GA, Nakatsuji H, Caricato M, Li X, Hratchian HP, Izmaylov AF, Bloino J, Zheng G, Sonnenberg JL, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Montgomery JAJr, Peralta JE, Ogliaro F, Bearpark M, Heyd JJ, Brothers E, Kudin KN, Staroverov VN, Kobayashi R, Normand J, Raghavachari K, Rendell A, Burant JC, Iyengar SS, Tomasi J, Cossi M, Rega N, Millam NJ, Klene M, Knox JE, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Martin RL, Morokuma K, Zakrzewski VG, Voth GA, Salvador P, Dannenberg JJ, Dapprich S, Daniels AD, Farkas Ö, Foresman JB, Ortiz JV, Cioslowski J, Fox DJ (2009) Gaussian 09, revision C.01. Gaussian, Inc., WallingfordGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2016

Authors and Affiliations

  1. 1.College of Chemistry and Material ScienceShandong Agricultural UniversityTaianPeople’s Republic of China
  2. 2.Department of ChemistryTaishan UniversityTaianPeople’s Republic of China

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