Download PDF
Synthesis 2019; 51(02): 450-462
DOI: 10.1055/s-0037-1610285
paper
© Georg Thieme Verlag Stuttgart · New York

DFT-Assisted Design and Evaluation of Bifunctional Amine/Pyridine-Oxazoline Metal Catalysts for Additions of Ketones to Unactivated Alkenes and Alkynes

Eric Greve
,
Jacob D. Porter
,
Chris Dockendorff  *
Department of Chemistry, Marquette University, P. O. Box 1881, Milwaukee, WI 53201-1881, USA   Email: christopher.dockendorff@mu.edu
› Author AffiliationsAmerican Chemical Society Petroleum Research Fund (55732-DNI1)
Further Information

Publication History

Received: 19 July 2018

Accepted: 28 August 2018

Publication Date:
02 October 2018 (online)

    Permissions and Reprints All articles of this category


Abstract

Bifunctional catalyst systems for the direct addition of ­ketones to unactivated alkenes/alkynes were designed and modeled by density functional theory (DFT). The designed catalysts possess bidentate ligands suitable for binding of pi-acidic group 10 metals capable of activating alkenes/alkynes, and a tethered organocatalyst amine to ­activate the ketone via formation of a nucleophilic enamine intermediate. The structures of the designed catalysts before and after C–C bond formation were optimized using DFT, and reaction steps involving group 10 metals were predicted to be significantly exergonic. A novel oxazoline precatalyst with a tethered amine separated by a meta-substituted benzene spacer was synthesized via a 10-step sequence that ­includes a key regioselective epoxide ring-opening step. It was combined with group 10 metal salts, including cationic Pd(II) and Pt(II), and screened for the direct addition of ketones to several alkenes and an ­internal alkyne. 1H NMR studies suggest that catalyst-catalyst inter­actions with this system via amine–metal coordination may preclude the desired addition reactions. The catalyst design approach disclosed here, and the promising calculations obtained with square planar group 10 metals, light a path for the discovery of novel bifunctional catalysts for C–C bond formation.

Key words

alkylation - alkene complexes - platinum - bifunctional ­catalysis - organocatalysis - ketones - DFT - catalyst design

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/s-0037-1610285. Included are 1H and 13C NMR spectra, representative Gaussian input files, and Cartesian coordinates for select DFT-optimized structures; Figure S1: DFT optimized cis/trans ethylene coordination for precatalyst 1; Figure S2: DFT optimized Cu(I) intermediates for Table 2, entry 12; Figure S3: Conformational sampling of DFT optimized 1-complex; Table S1: Complete set of DFT calculations for C–C bond formation with variable tether lengths and positions, with both Pd and Pt; Table S2: DFT calculations for intramolecular coordination of amine to metal center for various tether lengths and positions; Table S3: DFT calculations of structures with fixed distances between enamine and ethylene.
  • Supporting Information
 

  • References

  • 1 McCartney D. Guiry PJ. Chem. Soc. Rev. 2011; 40: 5122
    CrossrefPubMed
  • 2 Xu S. Negishi E.-I. Acc. Chem. Res. 2016; 49: 2158
    CrossrefPubMed
  • 3 Hack D. Blumel M. Chauhan P. Philipps AR. Enders D. Chem. Soc. Rev. 2015; 44: 6059
    CrossrefPubMed
  • 4 Binder JT. Crone B. Haug TT. Menz H. Kirsch SF. Org. Lett. 2008; 10: 1025
    CrossrefPubMed
  • 5 Yang T. Ferrali A. Campbell L. Dixon DJ. Chem. Commun. 2008; 2923
    PubMed
  • 6 Jensen KL. Franke PT. Arróniz C. Kobbelgaard S. Jørgensen KA. Chem. Eur. J. 2010; 16: 1750
    CrossrefPubMed
  • 7 Xiao Y.-P. Liu X.-Y. Che C.-M. Angew. Chem. Int. Ed. 2011; 50: 4937
    CrossrefPubMed
  • 8 Montaignac B. Vitale MR. Michelet V. Ratovelomanana-Vidal V. Org. Lett. 2010; 12: 2582
    CrossrefPubMed
  • 9 Montaignac B. Vitale MR. Ratovelomanana-Vidal V. Michelet V. J. Org. Chem. 2010; 75: 8322
    CrossrefPubMed
  • 10 Montaignac B. Vitale MR. Ratovelomanana-Vidal V. Michelet V. Eur. J. Org. Chem. 2011; 3723
  • 11 Montaignac B. Praveen C. Vitale MR. Michelet V. Ratovelomanana-Vidal V. Chem. Commun. 2012; 48: 6559
    PubMed
  • 12 Wang X. Widenhoefer RA. Chem. Commun. 2004; 660
    PubMed
  • 13 Cucciolito ME. D’Amora A. Vitagliano A. Organometallics 2010; 29: 5878
    Crossref
  • 14 Geier MJ. Gagné MR. J. Am. Chem. Soc. 2014; 136: 3032
    CrossrefPubMed
  • 15 Nguyen H. Gagné MR. ACS Catal. 2014; 4: 855
    CrossrefPubMed
  • 16 Walsh PJ. Kozlowski MC. Fundamentals of Asymmetric Catalysis USA), 2009
  • 17 Mo F. Dong G. Science 2014; 345 (6192): 68
    CrossrefPubMed
  • 18 Mo F. Lim HN. Dong G. J. Am. Chem. Soc. 2015; 137: 15518
    CrossrefPubMed
  • 19 Jira R. Angew. Chem. Int. Ed. 2009; 48: 9034
    CrossrefPubMed
  • 20 McDonald RI. Liu G. Stahl SS. Chem. Rev. 2011; 111: 2981
    CrossrefPubMed
  • 21 Sigman MS. Werner EW. Acc. Chem. Res. 2012; 45: 874
    CrossrefPubMed
  • 22 Melchiorre P. Marigo M. Carlone A. Bartoli G. Angew. Chem. Int. Ed. 2008; 47: 6138
    CrossrefPubMed
  • 23 Fürstner A. Acc. Chem. Res. 2014; 47: 925
    CrossrefPubMed
  • 24 Porter JD. Greve E. Alsafran A. Benoit AR. Lindeman SV. Dockendorff C. Tetrahedron 2018; 74: 4823 ; ChemRxiv 2018, https://doi.org/10.26434/chemrxiv.6163430.v1
    Crossref
  • 25 Stephan DW. Science 2016; 354 (6317): aaf7229
    CrossrefPubMed
  • 26 Hay PJ. Wadt WR. J. Chem. Phys. 1985; 82: 270
    Crossref
  • 27 Kendall RA. Dunning TH. Jr. Harrison RJ. J. Chem. Phys. 1992; 96: 6796
    Crossref
  • 28 Yoon NM. Brown HC. J. Am. Chem. Soc. 1968; 90: 2927
    Crossref
  • 29 Leung C, Tomaszewski MJ, Woo S. PCT Int. Appl WO 04 60882, 2004 ; Chem. Abstr. 2004, 141, 140172.
  • 30 Molander GA, Brown AR. J. Org. Chem. 2006; 71: 9681
    CrossrefPubMed
  • 31 Wang H.-Y, Huang K, De Jesús M, Espinosa S, Piñero-Santiago LE, Barnes CL, Ortiz-Marciales M. Tetrahedron: Asymmetry 2016; 27: 91
    CrossrefPubMed
  • 32 Lal GS, Pez GP, Pesaresi RJ, Prozonic FM, Cheng H. J. Org. Chem. 1999; 64: 7048
    Crossref
  • 33 Phillips AJ, Uto Y, Wipf P, Reno MJ, Williams DR. Org. Lett. 2000; 2: 1165
    CrossrefPubMed
  • 34 Stork G, Brizzolara A, Landesman H, Szmuszkovicz J, Terrell R. J. Am. Chem. Soc. 1963; 85: 207
    Crossref
  • 35 de Renzi A, Panunzi A, Vitagliano A, Paiaro G. J. Chem. Soc., Chem. Commun. 1976; 47
  • 36 Sen A, Lai T.-W. J. Am. Chem. Soc. 1981; 103: 4627
    Crossref
  • 37 Albietz PJ, Yang K, Lachicotte RJ, Eisenberg R. Organometallics 2000; 19: 3543
    Crossref
  • 38 Delort E, Velluz A, Frérot E, Rubin M, Jaquier A, Linder S, Eidman KF, MacDougall BS. J. Agric. Food Chem. 2011; 59: 11752
    CrossrefPubMed
  • 39 Hanwell MD, Curtis DE, Lonie DC, Vandermeersch T, Zurek E, Hutchison GR. J. Cheminform. 2012; 4: 17
    CrossrefPubMed
  • 40 Kowacs T, O’Reilly L, Pan Q, Huijser A, Lang P, Rau S, Browne WR, Pryce MT, Vos JG. Inorg. Chem. 2016; 55: 2685
    CrossrefPubMed