Gold(I)-Catalyzed Intramolecular C(sp3)–H Bond Functionalization

Rubén Miguélez; Omar Arto; Carlos Rodríguez-Arias; Pablo Barrio

doi:10.1055/a-2389-7434

Synthesis, Table of Contents

Synthesis 2025; 57(06): 1138-1152
DOI: 10.1055/a-2389-7434

short review

Special Topic Dedicated to Prof. Erick Carreira

Gold(I)-Catalyzed Intramolecular C(sp3)–H Bond Functionalization

Authors

Rubén Miguélez‡
Omar Arto‡
Carlos Rodríguez-Arias‡
Pablo Barrio∗

Abstract

All articles of this category

Dedicated to Prof. Carreira on the occasion of his 60^th birthday

Abstract

The merger of two of the most rapidly growing fields in catalysis, namely gold-catalysis and C–H activation/functionalization has resulted in major breakthroughs, affording unprecedented transformations. This review covers the most relevant contributions in this field during the last 10 years, restricted to the intramolecular functionalization of C(sp³)–H bonds.

1 Introduction

2 Carbene/Vinylidene Insertion

3 [1,5]-H Shift

4 Gold-Stabilized Vinyl Cation Mediated

5 Summary and Outlook

Key words

gold-catalysis - C–H functionalization - cyclization - carbene insertion - [1,5]-hydride shift - vinyl cation

Full Text

References

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60b Mackenroth AV, Ahrens A, Wunsch JF, Berger R, Rominger F, Rudolph M, Hashmi AS. K. Adv. Synth. Catal. 2024; 366: 1331
60c Tsuno H, Shen J, Komatsu H, Arichi N, Inuki S, Ohno H. Angew. Chem. Int. Ed. 2023; 62: e202307532
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60e Corcoran JC, Guo R, Xia Y, Wang Y.-M. Chem. Commun. 2022; 58: 11523
60f 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

61 Cai P.-J, Wang Y, Liu C.-H, Yu Z.-X. Org. Lett. 2014; 16: 5898
62 Wang Y, Cai P.-J, Yu Z.-X. J. Am. Chem. Soc. 2020; 142: 2777

63a Cao Z, Gagosz F. Angew. Chem. Int. Ed. 2013; 52: 9014
63b Rao W, Sally, Berry SN, Chan PW. H. Chem. Eur. J. 2014; 20: 13174
63c Onizawa Y, Hara M, Hashimoto T, Kusama H, Iwasawa N. Chem. Eur. J. 2010; 16: 10785
63d Kim SY, Park Y, Chung YK. Angew. Chem. Int. Ed. 2010; 49: 415
63e Kusama H, Onizawa Y, Iwasawa N. J. Am. Chem. Soc. 2006; 128: 16500

For Cope rearrangement of cis-alkenylalkynylcyclopropanes, see:

64a Gorin DJ, Watson ID. G, Toste FD. J. Am. Chem. Soc. 2008; 130: 3736
64b Ohe K, Yokoi T, Miki K, Nishino F, Uemura S. J. Am. Chem. Soc. 2002; 124: 526
64c Dolbier WR. Jr, Garza OT, Al-Sader BH. J. Am. Chem. Soc. 1975; 97: 5038

65 Zheng Z, Zhang L. Org. Chem. Front. 2015; 2: 1556

66a Li L, Shu C, Zhou B, Yu Y.-F, Xiao X.-Y, Ye L.-W. Chem. Sci. 2014; 5: 4057
66b Dateer RB, Pati K, Liu R.-S. Chem. Commun. 2012; 48: 7200
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67a Bucher J, Wurm T, Farshadfar K, Schukin M, Uzunidis G, Rudolph M, Rominger F, Ariafard A, Hashmi AS. K. Adv. Synth. Catal. 2023; 365: 3320
67b Ahrens A, Schwarz J, Lustosa DM, Pourkaveh R, Hoffmann M, Rominger F, Rudolph M, Dreuw A, Hashmi AS. K. Chem. Eur. J. 2020; 26: 5280
67c Claus V, Molinari L, Büllmann S, Thusek J, Rudolph M, Rominger F, Hashmi AS. K. Chem. Eur. J. 2019; 25: 9385
67d Plajer AJ, Ahrens L, Wieteck M, Lustosa DM, Babaahmadi R, Yates B, Ariafard A, Rudolph M, Rominger F, Hashmi AS. K. Chem. Eur. J. 2018; 24: 10766
67e Greisch J.-F, Weis P, Brendle K, Kappes MM, Haler JR. N, Far J, De Pauw E, Albers C, Bay S, Wurm T, Rudolph M, Schulmeister J, Hashmi AS. K. Organometallics 2018; 37: 1493
67f Bucher J, Stößer T, Rudolph M, Rominger F, Hashmi AS. K. Angew. Chem. Int. Ed. 2015; 54: 1666
67g Larsen MH, Houk KN, Hashmi AS. K. J. Am. Chem. Soc. 2015; 137: 10668
67h Yu C, Chen B, Zhou T, Tian Q, Zhang G. Angew. Chem. Int. Ed. 2015; 54: 10903
67i Hashmi AS. K, Lauterbach T, Nösel P, Vilhelmsen MH, Rudolph M, Rominger F. Chem. Eur. J. 2013; 19: 1058
67j Hashmi AS. K, Wieteck M, Braun I, Rudolph M, Rominger F. Angew. Chem. Int. Ed. 2012; 51: 10633

68 Wurm T, Bucher J, Duckworth S, Rudolph M, Rominger F, Hashmi AS. K. Angew. Chem. Int. Ed. 2017; 56: 3364
69 Wurm T, Bucher J, Rudolph M, Rominger F, Hashmi AS. K. Adv. Synth. Catal. 2017; 359: 1637

For recent examples, see:

70a Zhao F, Abdellaoui M, Hagui W, Ballarin-Marion M, Berthet J, Corcé V, Delbaere S, Dossmann H, Espagne A, Forté J, Jullien L, Le Saux T, Mouriès-Mansuy V, Ollivier C, Fensterbank L. Nat. Commun. 2022; 13: 2295
70b Wu J, Wei C, Zhao F, Du W, Geng Z, Xia Z. J. Org. Chem. 2022; 87: 14374
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70e Sarmiento JT, Cárcel M, Ramírez de Arellano C, Varea T, Asensio G, Olmos A. J. Org. Chem. 2022; 87: 3114
70f Kreuzahler M, Haberhauer G. Angew. Chem. Int. Ed. 2020; 59: 9433
70g García-Fernández PD, Iglesias-Sigüenza J, Rivero-Jerez PS, Díez E, Gómez-Bengoa E, Fernández R, Lassaletta JM. J. Am. Chem. Soc. 2020; 142: 16082
70h Kreuzahler M, Haberhauer G. Angew. Chem. Int. Ed. 2020; 59: 17739
70i de Orbe ME, Zanini M, Quinonero O, Echavarren AM. ACS Catal. 2019; 9: 7817
70j Kreuzahler M, Daniels A, Wölper C, Haberhauer G. J. Am. Chem. Soc. 2019; 141: 1337
70k Kreuzahler M, Haberhauer G. J. Org. Chem. 2019; 84: 8210
70l Bai Y.-B, Luo Z, Wang Y, Gao J.-M, Zhang L. J. Am. Chem. Soc. 2018; 140: 5860

71 Miguélez R, Semleit N, Rodríguez-Arias C, Mykhailiuk P, González JM, Haberhauer G, Barrio P. Angew. Chem. Int. Ed. 2023; 62: e202305296
72 For a recent review on the synthesis of the cyclopentene core, see: Miguélez R, Barrio P, González JM. Chem. Rec. 2023; 23: e202300254
73 For a synthetic application of the obtained 1-bromocyclopentene derivatives, see: Miguélez R, Arto O, Rodríguez-Arias C, del Blanco A, Barrio P, González JM. Eur. J. Org. Chem. 2024; 27: e202301274
74 Miguélez R, Arto O, Semleit N, Haberhauer G, Barrio P. Adv. Synth. Catal. 2024; 366: 780
75 Recently, a propargyl C–H functionalization with the intermediacy of a gold allenylidene has been disclosed: Wei Y, Jiang J, Jing Y, Ke Z, Zhang L. Angew. Chem. Int. Ed. 2024; 63: e202402286