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A theoretical study on synthesis mechanisms of α,β-unsaturated carbon γ-amino ester catalyzed by PPh3

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Abstract

In this paper, generation mechanism of α,β-unsaturated carbon γ-amino esters catalyzed by triphenylphosphine (PPh3) have been investigated using density functional theory (DFT). Two possible mechanisms (Mechanism A and Mechanism B) are proposed, in which there are three possible reaction pathways (Path A1/A2/A3 in Mechanism A and Path B1/B2/B3 in Mechanism B) except for the generation of the intermediate M1. The calculated results demonstrate that the energy favorable pathways (Path A2 and Path B2) include three process: the first step is an intermolecular proton transfer accompanied by a nucleophilic attack, the second step is an intramolecular proton transfer process, and the last step is the dissociation of PPh3 and the product generation. Furthermore, the reaction pathway associated with the E-isomer is the most favorable pathway and leads to the main product (E-P), which is in good agreement with the experimental results. This work might be helpful for understanding the significant roles of catalyst PPh3 and thus provide valuable insights on the rational design of potential catalysts for this kind of reactions.

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References

  1. 1.

    Cheong PH, Legault CY, Um JM, Celebi-Olcum N, Houk KN (2011) Quantum mechanical investigations of organocatalysis: mechanisms, reactivities, and selectivities Chem Rev 111:5042–5137

  2. 2.

    Zhang L, Liu HL, Qiao GY, Hou ZF, Liu Y, Xiao YM, Guo HC (2015) Phosphine-catalyzed highly enantioselective [3 + 3] cycloaddition of morita-baylis-hillman carbonates with C, N-cyclic azomethine imines J Am Chem Soc 137:4316–4319

  3. 3.

    Gomez C, Gicquel M, Carry JC, Schio L, Retailleau P, Voituriez A, Marinetti A (2013) Phosphine-catalyzed synthesis of 3,3-spirocyclopenteneoxindoles from γ-substituted allenoates: systematic studies and targeted applications J Organomet Chem 78:1488–1496

  4. 4.

    Jones RA, Krische MJ (2009) Asymmetric total synthesis of the iridoid β-glucoside (+)-geniposide via phosphine organocatalysis Org Lett 11:1849–1851

  5. 5.

    Kalek M, Fu GC (2015) Phosphine-catalyzed doubly stereoconvergent γ-additions of racemic heterocycles to racemic allenoates: the catalytic enantioselective synthesis of protected α,α-disubstituted α-amino acid derivatives J Am Chem Soc 137:9438–9442

  6. 6.

    Li EQ, Huang Y, Liang L, Xie PZ (2013) Phosphine-catalyzed [4 + 2] annulation of γ-substituent allenoates: facile access to functionalized spirocyclic skeletons Org Lett 15:3138–3141

  7. 7.

    Qin Z, Liu W, Wang D, He Z (2016) Phosphine-catalyzed (4 + 1) annulation of o-hydroxyphenyl and o-aminophenyl ketones with allylic carbonates: syntheses and transformations of 3-hydroxy-2,3-disubstituted dihydrobenzofurans and indolines J Organomet Chem 81:4690–4700

  8. 8.

    Johnson T, Pultar F, Menke F, Lautens M (2016) Palladium-catalyzed α-arylation of vinylogous esters for the synthesis of γ,γ-disubstituted cyclohexenones Org Lett 18:6488–6491

  9. 9.

    Zhou QF, Zhang K, Kwon O (2015) Stereoselective syntheses of α,β-unsaturated γ-amino esters through phosphine-catalyzed γ-umpolung additions of sulfonamides to γ-substituted allenoates Tetrahedron Lett 56:3273–3276

  10. 10.

    Clerc J, Schellenberg B, Groll M, Bachmann AS, Huber R, Dudler R, Kaiser M (2010) Convergent synthesis and biological evaluation of syringolin a and derivatives as eukaryotic 20s proteasome inhibitors Eur J Org Chem 2010:3991–4003

  11. 11.

    E. J, Coleman E, Silva DD, Kong F, Andersen RJ (1995) Cytotoxic peptides from the marine sponge cymbastela sp Pergamon 51:10653–10662

  12. 12.

    Linington RG, Clark BR, Trimble EE, Almanza A, Urena L-D, Kyle DE, Gerwick WH (2009) Antimalarial peptides from marine cyanobacteria: isolation and structural elucidation of gallinamide a J Nat Prod 72:14–17

  13. 13.

    Wang Y, Tang MS, Wang YY, Wei DH (2016) Insights into stereoselective aminomethylation reaction of α,β-unsaturated aldehyde with N,O-acetal via n-heterocyclic carbene and bronsted acid/base cooperative organocatalysis J Organomet Chem 81:5370–5380

  14. 14.

    Zhang XL, Tang MS, Wang Y, Ran YY, Wei DH, Zhu YY, Zhang WJ (2016) DFT study on the mechanism and stereoselectivity of NHC-catalyzed synthesis of substituted trifluoromethyl dihydropyranones with contiguous stereocenters J Organomet Chem 81:868–877

  15. 15.

    Creech GS, Zhu XF, Fonovic B, Dudding T, Kwon O (2008) Theory-guided design of Bronsted acid-assisted phosphine catalysis: synthesis of dihydropyrones from aldehydes and allenoates Tetrahedron 64:6935–6942

  16. 16.

    Li SJ, Tang HB, Wang Y, Zhu YY, Fang DC, Wei DH, Tang MS (2015) A DFT study on the competing mechanisms of pph3-catalyzed [3+3] and [3+2] annulations between 5-acetoxypenta-2,3-dienoate and 1C,3O-bisnucleophiles J Mol Catal A: Chem 407:137–146

  17. 17.

    Martin K, Stefan G (2009) “Mindless” DFT benchmarking J Chem Theory Comput 5:993–1003

  18. 18.

    Zhao Y, Truhlar DG (2011) Density functional theory for reaction energies: test of meta and hybrid meta functionals, range-separated functionals, and other high-performance functionals J Chem Theory Comput 12:669–676

  19. 19.

    Li YX, Zhu YY, Zhang WJ, Wei DH, Ran YY, Zhao QL, Tang MS (2014) A DFT study on the reaction mechanism of dimerization of methyl methacrylate catalyzed by N-heterocyclic carbene Phys Chem Chem Phys 16:20001–20008

  20. 20.

    Wang Y, Wu BH, Zheng LJ, Wei DH, Tang MS (2016) DFT perspective toward [3 + 2] annulation reaction of enals with α-ketoamides through NHC and brønsted acid cooperative catalysis: mechanism, stereoselectivity, and role of NHC Org Chem Front 3:190–203

  21. 21.

    Liu T, Han S, Li YP, Bi SW (2016) Theoretical insight into the mechanisms and regioselectivity of [4 + 3] and [4 + 1] annulations of enals with azoalkenes catalyzed by n-heterocyclic carbenes J Organomet Chem 81:9775–9784

  22. 22.

    Pareek M, Sunoj RB (2016) Mechanism and stereoselectivity in an asymmetric n-heterocyclic carbene-catalyzed carbon-carbon bond activation reaction Org Lett 18:5932–5935

  23. 23.

    Zhao L, Zhang L, Fang DC (2016) DFT study on rhodium-catalyzed intermolecular [2 + 2] cycloaddition of terminal alkynes with electron-deficient alkenes Organometallics 35:3577–3586

  24. 24.

    Abdolmaleki A, Tavakol H, Molavian MR, Firouz K (2014) Synthesis, FT-IR, NMR and DFT analysis of a new salophen based on diaminophenazine moiety J Mol Struct 1062:44–47

  25. 25.

    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, Peralta JE, Ogliaro F, Bearpark M, Heyd JJ, Brothers E, Kudin KN, Staroverov VN, Keith T, Kobayashi R, Normand J, Raghavachari K, Rendell A, Burant JC, Iyengar SS, Tomasi MC, Rega JMM, Klene M, Knox JE, Cross JB, Bakken CA, Jaramillo GR, Stratmann OY, Austin R, Cammi CP, Ochterski RLM, Morokuma VGZ, Voth GA, Salvador JJD P, Dapprich S, Daniels AD, Farkas O, Foresman JB, Ortiz JV, Cioslowski J, Fox DJ (2010) Gaussian 09, Revision C.01. Gaussian Inc., Wallingford,

  26. 26.

    Ameer FS, Pittman CU, Zhang DM (2013) Quantification of resonance Raman enhancement factors for rhodamine 6g (r6g) in water and on gold and silver nanoparticles: implications for single-molecule r6g sers J Phys Chem C 117:27096–27104

  27. 27.

    Batalović K, Koteski V, Stojić D (2013) Hydrogen storage in martensite Ti–Zr–Ni alloy: a density functional theory study J Phys Chem C 117:26914–26920

  28. 28.

    Ruiz E (2008) Exchange coupling constants using density functional theory: the M0X suite Chem Phys Lett 460:336–338

  29. 29.

    Wei DH, Tang MS, Zhan CG (2015) Fundamental reaction pathway and free energy profile of proteasome inhibition by syringolin A (sylA) Org Biomol Chem 13:6857–6865

  30. 30.

    Valero R, Costa R, Moreira IDPR, Truhlar DG, Illas F (2008) Performance of the M06 family of exchange-correlation functionals for predicting magnetic coupling in organic and inorganic molecules J Chem Phys 128:114103

  31. 31.

    Zhao Y, Truhlar DG (2009) Benchmark energetic data in a model system for grubbs ii metathesis catalysis and their use for the development, assessment, and validation of electronic structure methods J Chem Theory Comput 5:324–333

  32. 32.

    Deepa I, Kumar SN, Sreerag RS, Nath VS, Mohandas C (2015) Purification and synergistic antibacterial activity of arginine derived cyclic dipeptides, from Achromobacter sp. associated with a rhabditid entomopathogenic nematode against major clinically relevant biofilm forming wound bacteria Front Microbiol 6:1–16

  33. 33.

    Gonzalez C, Schlegel BH (1990) Reaction path following in mass-weighted internal coordinates J Phys Chem 14:5523–5527

  34. 34.

    Mennucci B, Tomasi J (1997) Continuum solvation models: a new approach to the problem of solute’s charge distribution and cavity boundaries J Chem Phys 106:5151

  35. 35.

    Zhang WJ, Zhu YY, Wei DH, Li YX, Tang MS (2012) Theoretical investigations toward the [4 + 2] cycloaddition of ketenes with n-benzoyldiazenes catalyzed by n-heterocyclic carbenes: mechanism and enantioselectivity J Organomet Chem 77:10729–10737

  36. 36.

    Zhu YY, Li YX, Zhang WJ, Zhao QL, Tang MS (2013) DFT study on reaction mechanisms of propylamine and dimethyl acetylenedicarboxylate with 1,3-dimethylalloxan Comput Theor Chem 1004:47–55

  37. 37.

    Sun DZ, Zhu YY, Wei DH, Zhang C, Zhang WJ, Tang MS (2010) Insight into the multicomponent reaction mechanisms of prop-2-en-1-amine and ethyl propiolate with alloxan derivative: a density functional theory study Chem Phys Lett 495:33–39

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Acknowledgments

The authors acknowledge financial support from the National Natural Science Foundation of China (Nos. 21001095 and J120062), University Key Research Programs of Department of Education in Henan Province (Grant Nos. 15A150082 and 14A150033), and Training Foundation of Zhengzhou University Innovation & Enterprise Capability of College Student (No. 2016xjxm264).

Author information

Correspondence to Yanyan Zhu.

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Ethical statement/conflict of interest

The authors declare that they have no conflict of interest. All procedures performed in studies involving human participants were in accordance with the ethical standards of the institutional and/or national research committee and with the 1964 Helsinki declaration and its later amendments or comparable ethical standards. This article does not contain any studies with animals performed by any of the authors.

Electronic Supplementary Materials

Figure S1

Energy profile of PPh3 elimination occurring before proton transfer. (DOCX 274 kb)

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Xu, H., Li, Y., Zhu, Y. et al. A theoretical study on synthesis mechanisms of α,β-unsaturated carbon γ-amino ester catalyzed by PPh3 . Struct Chem 28, 1959–1968 (2017). https://doi.org/10.1007/s11224-017-0990-3

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Keywords

  • Reaction mechanism
  • Triphenylphosphine
  • Amino ester
  • DFT