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

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

Key words

carbocations - weakly coordinating anions - C–H insertion reactions - catalysis - C–H functionalization - organocatalysis

Publikationsverlauf

Eingereicht: 22. Mai 2020

Angenommen: 03. Juni 2020

Artikel online veröffentlicht:
24. September 2020

• 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
• 2a Nuyken O, Pask SD. Polymers 2013; 5: 361
• 2b Bisht HS, Chatterjee AK. J. Macromol. Sci., Polym. Rev. 2007; 41: 139
• 2c Christianson DW. Chem. Rev. 2006; 106: 3412
• 2d Lednicer D. The Organic Chemistry of Drug Synthesis, Vol. 7. Wiley; Hoboken: 2008
• 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