Synlett
DOI: 10.1055/s-0040-1707908
synpacts

C–H Functionalization Reactions of Phenyl and Vinyl Carbocations Paired with Weakly Coordinating Anions

Stasik Popov
,
Brian Shao
,
Alex L. Bagdasarian
,
Benjamin Wigman
,
Hosea M. Nelson
Department of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, CA, 90095, USA   Email: hosea@chem.ucla.edu
› Author Affiliations
Support was generously provided by UCLA, the David and Lucile Packard foundation (to H.M.N.), the PEW charitable trusts (to H.M.N.), the NIH-NIGMS (R35 GM128936 to H.M.N.), and the Alfred P. Sloan foundation (to H.M.N.). A.L.B, S.P., and B.W. thank the Christopher S. Foote fellowship for funding. S.P. and B.W. thank the National Science Foundation (DGE-1650604) for funding.


Abstract

Carbocations have played a central role in the chemical sciences for over a century. In a synthetic setting, most methods utilize stabilized tricoordinate carbocations, while there are far fewer examples of reactions featuring nonstabilized dicoordinate cations. Here, we provide an overview of recent developments in the generation of high-energy carbocations mediated by weakly coordinating anions and the C–H insertion reactions of such carbocations. Moreover, we discuss mechanistic studies of these catalytic C–H insertion reactions aimed at furthering our understanding of the reactive nature of these rarely invoked cationic intermediates.

1 Introduction

2 Background: Phenyl Carbocations

3 Silylium/Carborane-Catalyzed C–H Insertion Reactions of Phenyl Carbocations

4 Silane-Fueled, Weakly Coordinating Anion-Catalyzed, Reductive C–H Insertion Reactions of Vinyl Carbocations

5 C–H Insertion Reactivity of Vinyl Carbocations under Basic Conditions

6 Conclusion and Outlook



Publication History

Received: 22 May 2020

Accepted: 03 June 2020

Publication Date:
24 September 2020 (online)

© 2020. Thieme. All rights reserved

Georg Thieme Verlag KG
Rüdigerstraße 14, 70469 Stuttgart, Germany

 
  • References

    • 1a Hassan J, Sévignon M, Gozzi C, Schulz E, Lemaire M. Chem. Rev. 2002; 102: 1359
    • 1b Magano J, Dunetz JR. Chem. Rev. 2011; 111: 2177
    • 3a Christianson DW. Chem. Rev. 2006; 106: 3142
    • 3b Ruzicka L. Experientia 1953; 9: 357
    • 3c Reed CA. Chem. Commun. 2005; 1669
    • 4a Pronin SV, Shenvi RA. Nat. Chem. 2012; 4: 915
    • 4b Zhang Q, Tiefenbacher K. Nat. Chem. 2015; 7: 197
    • 5a Reed CA. Acc. Chem. Res. 2010; 43: 121
    • 5b Kato T, Reed CA. Angew. Chem. Int. Ed. 2004; 43: 2908
  • 6 Burch J, Bagdasarian AL, Hooshmand T, Nelson HM. ChemRxiv, 2020 https://chemrxiv.org/articles/preprint/Terpene_Tail-to-Head_Polycyclization_Mediated_by_Small_Molecule_Catalysts_A_Weakly-Coordinating_Anion_Approach/12719780.
  • 7 Olah GA. J. Org. Chem. 2001; 66: 5943
    • 8a Zollinger H. Acc. Chem. Res. 1973; 6: 335
    • 8b Wu Z, Glaser R. J. Am. Chem. Soc. 2004; 126: 10632
  • 9 Mascarelli L. Gazz. Chim. Ital. 1936; 66: 843
  • 10 Daudpota AS, Heaney H. Tetrahedron Lett. 1978; 19: 3471
  • 11 Fagnoni M, Albini A. Acc. Chem. Res. 2005; 38: 713
  • 12 Allemann O, Baldride KK, Siegel JS. Org. Chem. Front. 2015; 2: 1018
  • 13 Allemann O, Duttwyler S, Romanato P, Baldridge KK, Siegel JS. Science 2011; 332: 574
  • 14 Lambert JB. Tetrahedron 1990; 46: 2677
  • 15 Shao B, Bagdasarian AL, Popov S, Nelson HM. Science 2017; 355: 1403
  • 16 McMillen DF, Golden DM. Annu. Rev. Phys. Chem. 1982; 33: 493
    • 17a Hanack M. Acc. Chem. Res. 1970; 3: 209
    • 17b Stang PJ, Rappaport Z, Hanack M, Subramanian LR. Vinyl Cations . Academic Press; New York: 1979
    • 18a Biermann U, Koch R, Metzger JO. Angew. Chem. Int. Ed. 2006; 45: 3076
    • 18b Cleary SE, Hensinger MJ, Brewer M. Chem. Sci. 2017; 8: 6810
    • 18c Lee JW, Shin JY, Chun YS, Jang HB, Song CE, Lee S.-g. Acc. Chem. Res. 2010; 43: 985
    • 18d Yoon MY, Kim JH, Choi DS, Shin US, Lee JY, Song CE. Adv. Synth. Catal. 2007; 349: 1725
  • 19 Popov S, Shao B, Bagdasarian AL, Benton TR, Zou L, Yang Z, Houk KN, Nelson HM. Science 2018; 361: 381
  • 20 Stang PJ, Anderson A. J. Am. Chem. Soc. 1978; 100: 1520
  • 21 Körbe S, Schreiber PJ, Michl J. Chem. Rev. 2006; 106: 5208
  • 22 Wigman B, Popov S, Bagdasarian AL, Shao B, Benton TR, Williams CG, Fisher SP, Lavallo V, Houk KN, Nelson HM. J. Am. Chem. Soc. 2019; 141: 9140