Dearomative Carbonylations of Arenes via Bifunctional Coordination to Cr(CO)₃

Abstract

Carbonylation reactions serve as powerful tools to construct useful carbonyl compounds with high efficiency and atom economy. Compared with the well-developed carbonylation chemistry for alkenes, the dearomative carbonylation of arenes is largely underexplored, possibly owing to the severe challenge in overcoming resonance stabilization of arene π-systems. Bifunctional coordination to tricarbonylchromium not only offers a reliable strategy to activate inert benzene π-bonds towards dearomatizations but also provides the CO source for the carbonylation process. Herein, we highlight the recent progress in dearomative carbonylations of chromium-bound arenes through either the conventional nucleophile-electrophile addition mode or the newly-developed umpolung-enabled nucleophile-nucleophile addition mode under mild CO-gas-free conditions. Given the great abundance and diversity of arene substrates, we hope this review will attract more attention to this new direction of carbonylation chemistry.

1 Introduction

2 Dearomative Carbonylations of Arenes via Nucleophile-Electrophile Addition

3 Dearomative Carbonylations of Arenes via Nucleophile-Nucleophile Addition

4 Conclusion

Key words

arene - carbonylation - dearomatization - η⁶-coordination - chromium - aminocarbonylation - alkoxycarbonylation - carbamoylation

Publication History

Received: 25 September 2024

Accepted: 21 October 2024

Accepted Manuscript online:
21 October 2024

Article published online:
12 November 2024

• References

• 1 Colquhoun HM, Thompson DJ, Twigg MV. Carbonylation: Direct Synthesis of Carbonyl Compounds 1991
• 2a Wu X.-F, Fang X, Wu L, Jackstell R, Neumann H, Beller M. Acc. Chem. Res. 2014; 47: 1041
• 2b Peng J.-B, Wu F.-P, Wu X.-F. Chem. Rev. 2019; 119: 2090
• 2c Folster CP, Harkins RP, Lo S.-Y, Sachs JD, Tonks IA. Trends Chem. 2021; 3: 469
• 2d Cai S, Zhang H, Huang H. Trends Chem. 2021; 3: 218
• 3 Yang J, Liu J, Neumann H, Franke R, Jackstell R, Beller M. Science 2019; 366: 1514
• 4a Schreiber SL. Science 2000; 287: 1964
• 4b Tan D. Nat. Chem. Biol. 2005; 1: 74
• 4c Galloway W, Isidro-Llobet A, Spring D. Nat. Commun. 2010; 1: 80
• 5a Wertjes WC, Southgate EH, Sarlah D. Chem. Soc. Rev. 2018; 47: 7996
• 5b Huck CJ, Sarlah D. Chem 2020; 6: 1589
• 6 Liebov BK, Harman WD. Chem. Rev. 2017; 117: 13721
• 7 Pape AR, Kaliappan KP, Kündig EP. Chem. Rev. 2000; 100: 2917
• 8 Rosillo M, Domínguez G, Pérez-Castells J. Chem. Soc. Rev. 2007; 36: 1589
• 9 Wang M.-Y, Zeng W.-L, Chen L, Yuan Y.-F, Li W. Angew. Chem. Int. Ed. 2024; 63: e202403917
• 10 Kündig EP, Simmons DP. J. Chem. Soc., Chem. Commun. 1983; 1320
• 11a Kündig EP, Cunningham AF. Jr, Paglia P, Simmons DP, Bernardinelli G. Helv. Chim. Acta 1990; 73: 386
• 11b Kündig EP, Bernardinelli G, Liu R, Ripa A. J. Am. Chem. Soc. 1991; 113: 9676
• 11c Kündig EP, Bellido A, Kaliappan KP, Pape AR, Radix S. Synlett 2003; 2407
• 12a Kündig EP, Ripa A, Bernardinelli G. Angew. Chem., Int. Ed. Engl. 1992; 31: 1071
• 12b Kündig EP, Amurrio D, Anderson G, Beruben D, Khan K, Ripa A, Ronggang L. Pure Appl. Chem. 1997; 69: 543
• 13 Kündig EP, Cannas R, Laxmisha M, Liu R, Tchertchian S. J. Am. Chem. Soc. 2003; 125: 5642
• 14 The Amide Linkage: Structural Significance in Chemistry, Biochemistry, and Materials Science. Greenberg A, Breneman CM, Liebman JF. John Wiley & Sons; New York: 2000
• 15a Pattabiraman VR, Bode JW. Nature 2011; 480: 471
• 15b Allen CL, Williams JM. J. Chem. Soc. Rev. 2011; 40: 3405
• 15c de Figueiredo RM, Suppo J.-S, Campagne J.-M. Chem. Rev. 2016; 116: 12029
• 16 Wang M.-Y, Wu C.-J, Zeng W.-L, Jiang X, Li W. Angew. Chem. Int. Ed. 2022; 61: e202210312
• 17 Pfletschinger A, Koch W, Schmalz H.-G. New J. Chem. 2001; 25: 446
• 18a Lawrence SA. In Amines: Synthesis, Properties and Applications . Cambridge University Press; Cambridge: 2004
• 18b Amino Group Chemistry: From Synthesis to the Life Sciences. Ricci A. Wiley-VCH; Weinheim: 2008
• 19 Li Z.-J, Wang M.-Y, Li C.-Q, Zeng W.-L, Li W. Chem. Eur. J. 2023; 29: e202300776
• 20 Li C.-Q, Jiang X, Wang M.-Y, Zeng W.-L, Li W. CCS Chem. 2024; 6: 2066