Recent Progress on Catalytic Synthesis of Enantioenriched α-Arylated Ketones

doi:10.6023/cjoc202408031

Abstract

Enantioenriched α-arylated ketones are ubiquitous subunits in valuable target molecules and serve as versatile synthetic precursors for other functional groups. Thus, the development of catalytic syenthesis of asymmetric α-arylated ketones remains one of the research topics in organic chemistry and has attracted great attention from synthetic chemists. Over the past decades, great efforts have been devoted to the synthesis of enantioenriched α-arylated ketones. The recent progress of catalytic foramtion of enantioenriched α-arylated ketones is reviewed. Moreover, the future directions and efforts for further development of divese enabling catalytic means to directly and effectively obtain enantioenriched α-arylated ketones are discussed.

Key words: α-arylated ketone, asymmetric catalysis, cross-coupling reaction, transition-metal-catalysis, organocatalysis

Cite this article

Yiming Du, Junsong Jia, Yulong Li, Wei Shu. Recent Progress on Catalytic Synthesis of Enantioenriched α-Arylated Ketones[J]. Chinese Journal of Organic Chemistry, 2025, 45(6): 1838-1870.

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Fig. & Tab. 57

Figure 1. Representative molecules containing enantioenriched α-arylated ketones

Scheme 1. Catalytic methods to construct chiral α-arylated ketones

Scheme 2. Pd-catalyzed asymmetric α-arylation of cyclic ketones with aryl bromides

Scheme 3. Pd-catalyzed asymmetric α-arylation of ketone enolates

Scheme 4. Cu-catalyzed asymmetric coupling of N-acyl o-iodoanilines with β-ketone esters

Scheme 5. Pd or Ni-catalyzed asymmetric α-arylation of cyclic ketones with aryl triflates

Scheme 6. Ni-catalyzed asymmetric α-arylation of cyclic ketones with aryl chlorides

Scheme 7. Pd-catalyzed asymmetric α-arylation of cyclic α-fluoroketones

Scheme 8. Hydroacylation of alkenes and Ni-catalyzed asymmetric α-arylation cascade

Scheme 9. Electrochemical cobalt-and amine-cocatalyzed asymmetric α-arylation reaction of 1,3-dicarbonyl compounds

Scheme 10. Chiral primary amine-catalyzed α-arylation of β-diketones

Scheme 11. Chiral aza-bisoxazoline-zinc catalyzed retro-Claisen reaction

Scheme 12. Chiral phase-transfer-catalyst catalyzed asymmetric α-arylation of β-ketoamides with arynes

Scheme 13. Pd/L-proline catalyzed intramolecular asymmetric α-arylation of cyclohexanones

Scheme 14. Pd-catalyzed asymmetric α-arylative desymmetrization of 1,3-diketones

Scheme 15. Pd/amine co-catalyzed asymmetric α-arylative desymmetrization of cyclobutanones

Scheme 16. Pd-catalyzed asymmetric α-arylation of cyclic ketones

Scheme 17. Pd-catalyzed intramolecular asymmetric α-arylation of cyclic ketones to construct spirocycles with quaternary carbon stereocenters

Scheme 18. Chiral phosphoric acid catalyzed asymmetric addition of α-arylated cyclic ketones to allenamides

Scheme 19. Chiral phosphoric acid/Pd-catalyzed asymmetric α-allylation of α-aryl cyclic ketones

Scheme 20. Chiral phosphoric acid-catalyzed asymmetric additions of α-alkynyl-α-aryl ketones to allenamides

Scheme 21. Fe-catalyzed asymmetric α-alkylation of 2-acylimidazoles via dehydrogenative radical cross-coupling with akanes

Scheme 22. Chiral phosphoric acid catalyzed asymmetric amination of α-arylated cyclic ketones

Scheme 23. Chiral phosphate-catalyzed enantioselective amination of α-alkynyl α-aryl ketones

Scheme 24. Chiral phosphate-catalyzed kinetic resolution of racemic α-aryl alkynones for asymmetric aminations

Scheme 25. Chiral phosphoric acid-catalyzed asymmetric α-aryloxylation of α-aryl ketones with 1,4-benzoquinone

Scheme 26. Pd-catalyzed enantioselective arylation of ketones

Scheme 27. Enantioselective α-arylation of ketones via a novel Cu(I)-bis(phosphine) dioxide catalytic system

Scheme 28. Ni-catalyzed asymmetric cross-coupling of α-bromoketones with aryl zinc reagents

Scheme 29. Ni-catalyzed asymmetric cross-coupling of α-bromoketones with aryl Grignard reagents

Scheme 30. Ni-catalyzed asymmetric cross-coupling of α-bromo-α-fluoroketones with aryl zinc reagents

Scheme 31. Co-catalyzed asymmetric cross-coupling of α-bromo ketones with aryl zinc reagents

Scheme 32. Nickel-catalyzed asymmetric cross-coupling reactions of benzyl chlorides with acyl chlorides

Scheme 33. Chiral oxazaborolidinium ion catalytic asymmetric formal in-sertion of aryldiazoalkanes into the C—H bond of aldehydes

Scheme 34. Pd-catalyzed stereoconvergent cross-coupling of racemic benzylic zinc reagents with thioesters

Scheme 35. Visible-light mediated Ni-catalyzed benzylic asy-mmetric acylation

Scheme 36. Visible-light and Ni-catalyzed asymmetric acylation of benzylic C—H bond

Scheme 37. Ni-catalyzed multicomponent coupling: reductive hydrocarbonylation of alkenes

Scheme 38. Pd-catalyzed stereospecific cross-coupling of acyl chlorides with benzyl trifluoroborates

Scheme 39. Photoredox/Nickel-catalyzed enantioconvergent acylation of secondary alkyltrifuoroborate with anhydrides

Scheme 40. NHC-catalyzed asymmetric intramolecular hydroacylation of α-substituted styrene

Scheme 41. NHC-catalyzed enantioselective intramolecular hydroacylation of α-substituted styrenes

Scheme 42. CuH-catalyzed enantioselective reductive coupling of aryl alkenes and aryl carboxylic anhydrides

Scheme 43. CuH-catalyzed asymmetric hydroacylation of α,β-unsaturated carboxylic acids with aryl olefins

Scheme 44. Co-catalyzed enantio-and diastereoselective intramolecular hydroacylation of trisubstituted alkenes

Scheme 45. Pd-catalyzed asymmetric acyl-carbamoylation of alkenes

Scheme 46. Ligand relay catalysis enabled asymmetric migratory reductive acylation of alkenes

Scheme 47. Chiral N,N'-dioxide-Sc(OTf)3 complex catalyzed intramolecular asymmetric homologation of aryl ketones with α-diazo esters

Scheme 48. Rh-catalyzed asymmetric carbene insertion into B—H bonds

Scheme 49. Rh-catalyzed asymmetric hydroarylation of cylopent-4-ene-1,3-diones under base-free conditions

Scheme 50. Visible-light mediated, chiral phosphoric acid-catalyzed reductive cross coupling and enantioselective protonation of α-branched vinyl ketone with vinyl pyridine

Scheme 51. Visible-light and tertiary amine-catalyzed deracemization of α-arylpyridones

Scheme 52. Possible mechanism of visible-light and tertiary amine-catalyzed deracemization of α-arylpyridones

Scheme 53. Visible-light-induced, phosphoric acid catalyzed atroposelective synthesis of N-arylpyrroles

Scheme 54. Visible-light and phosphoric acid catalyzed enantioselective synthesis of α,α-diarylketones

Scheme 55. Chiral phosphoric acid catalyzed enantioselective synthesis of α,α-diaryl ketones

Scheme 56. Visible-light mediated, chiral phosphoric acid catalyzed radical-radical coupling and enantioselective protonation reaction

References 57

[1]	(a) Xu, Y.; Su, T.; Huang, Z.; Dong, G. Angew. Chem., Int. Ed. 2016, 55, 2559.
	(b) Hao, Y.-J.; Hu, X.-S.; Zhou, Y.; Zhou, J.; Yu, J.-S. ACS Catal. 2020, 10, 955.
	(c) Wei, X.; Wang, K.; Fang, W. Org. Biomol. Chem. 2023, 21, 3858.
[2]	(a) Johansson, C. C. C.; Colacot, T. J. Angew. Chem., Int. Ed. 2010, 49, 676.
	(b) Bellina, F.; Rossi, R. Chem. Rev. 2010, 110, 1082.
	(c) Orlandi, M.; Escudero-Casao, M.; Licini, G. Synthesis 2021, 53, 4559.
	(d) Culkin, D. A.; Hartwig, J. F. Acc. Chem. Res. 2003, 36, 234.
	(e) Burtoloso, A. C. B. Synlett 2009, 2009, 320.
	(f) Mazet, C. Synlett 2012, 23, 1999.
	(g) Vargová, D.; Némethová, I.; Plevová, K.; Šebesta, R. ACS Catal. 2019, 9, 3104.
[3]	Åhman, J.; Wolfe, J. P.; Troutman, M. V.; Palucki, M.; Buchwald, S. L. J. Am. Chem. Soc. 1998, 120, 1918.
[4]	Hamada, T.; Chieffi, A.; Åhman, J.; Buchwald, S. L. J. Am. Chem. Soc. 2002, 124, 1261.
[5]	Xie, X.; Chen, Y.; Ma, D. J. Am. Chem. Soc. 2006, 128, 16050.
[6]	Liao, X.; Weng, Z.; Hartwig, J. F. J. Am. Chem. Soc. 2008, 130, 195.
[7]	Ge, S.; Hartwig, J. F. J. Am. Chem. Soc. 2011, 133, 16330.
[8]	Jiao, Z.; Beiger, J. J.; Jin, Y.; Ge, S.; Zhou, J. S.; Hartwig, J. F. J. Am. Chem. Soc. 2016, 138, 15980.
[9]	Ghosh, A.; Walker, Jr., J, A.; Ellern, A.; Stanley, L. M. ACS Catal. 2016, 6, 2673.
[10]	Li, L.; Li, Y.; Fu, N.; Zhang, L.; Luo, S. Angew. Chem., Int. Ed. 2020, 59, 14347.
[11]	Han, Y.; Shi, M.; Mi, X.; Luo, S. Chem.-Eur. J. 2022, 28, e202202584.
[12]	Liu, J.-H.; Lv, X.-J.; Liu, Y.-K. Org. Lett. 2023, 25, 1706.
[13]	Pan, G.; Pu, M.; Wang, H.; Ying, M.; Li, Y.; Dong, S.; Feng, X.; Liu, X. J. Am. Chem. Soc. 2023, 145, 26318.
[14]	Liu, R.-R.; Li, B.-L.; Lu, Jun.; Shen, C.; Gao, J.-R.; Jia, Y.-X. J. Am. Chem. Soc. 2016, 138, 5198.
[15]	Zhu, C.; Wang, D.; Zhao, Y.; Sun, W.-Y.; Shi, Z. J. Am. Chem. Soc. 2017, 139, 16486.
[16]	Wang, M.; Chen, J.; Chen, Z.; Zhong, C.; Lu, P. Angew. Chem., Int. Ed. 2018, 57, 2707.
[17]	Rao, X.; Li, N.; Bai, H.; Dai, C.; Wang, Z.; Tang, W. Angew. Chem., Int. Ed. 2018, 57, 12328.
[18]	Wu, T.; Kang, X.; Bai, H.; Xiong, W.; Xu, G.; Tang, W. Org. Lett. 2020, 22, 4602.
[19]	Yang, X.; Toste, F. D. Chem. Sci. 2016, 7, 2653.
[20]	Pupo, G.; Properzi, R.; List, B. Angew. Chem., Int. Ed. 2016, 55, 6099.
[21]	Wang, J.; He, F.; Yang, X. Nat. Commun. 2021, 12, 6700.
[22]	Xu, N.; Pu, M.; Yu, H.; Yang, G.; Liu, X.; Feng, X. Angew. Chem., Int. Ed. 2024, 63, e202314256.
[23]	Yang, X.; Toste, F. D. J. Am. Chem. Soc. 2015, 137, 3205.
[24]	He, F.; Wang, J.; Zhou, F.; Tao, H.; Yang, X. Org. Chem. Front. 2021, 8, 5377.
[25]	He, F.; Shen, G.; Yang, X. Chin. J. Chem. 2022, 40, 15.
[26]	Shevchenko, G. A.; Oppelaar, B.; List, B. Angew. Chem., Int. Ed. 2018, 57, 10756.
[27]	Huang, Z.; Lim, L. H.; Chen, Z.; Li, Y.; Zhou, F.; Su, H.; Zhou, J. Angew. Chem., Int. Ed. 2013, 52, 4906.
[28]	Escudero-Casao, M.; Licini, G.; Orlandi, M. J. Am. Chem. Soc. 2021, 143, 3289.
[29]	Lundin, P. M.; Esquivias, J.; Fu, G. C. Angew. Chem., Int. Ed. 2009, 48, 154.
[30]	Lou, S.; Fu, G. C. J. Am. Chem. Soc. 2010, 132, 1264.
[31]	Yin, H.; Fu, G. C. J. Am. Chem. Soc. 2019, 141, 15433.
[32]	Liang, Y.; Fu, G. C. J. Am. Chem. Soc. 2014, 136, 5520.
[33]	Wang, J.; Shen, X.; Chen, X.; Bao, Y.; He, J.; Lu, Z. J. Am. Chem. Soc. 2023, 145, 24958.
[34]	Cherney, A. H.; Kadunce, N. T.; Reisman, S. E. J. Am. Chem. Soc. 2013, 135, 7442.
[35]	Kang, B. C.; Nam, D. G.; Hwang, G.-K.; Ryu, D. H. Org. Lett. 2015, 17, 4810.
[36]	Oost, R.; Misale, A.; Maulide, N. Angew. Chem., Int. Ed. 2016, 55, 4587.
[37]	Gandolfo, E.; Tang, X.; Roy, S. R.; Melchiorre, P. Angew. Chem., Int. Ed. 2019, 58, 16854.
[38]	Huan, L.; Shu, X. Zu, W.; Zhong, D.; Huo, H. Nat. Commun. 2021, 12, 3536.
[39]	Chen, J.; Zhu, S. J. Am. Chem. Soc. 2021, 143, 14089.
[40]	Roh, B.; Farah, A. O.; Kim, B.; Feoktistova, T.; Moeller, F.; Kim, K. D.; Cheong, P. H.-Y.; Lee, H. G. J. Am. Chem. Soc. 2023, 145, 7075.
[41]	Wang, W.; Shen, C.; Zhang, L.; Dong, K. Org. Lett. 2024, 26, 850.
[42]	Piel, I.; Steinmetz, M.; Hirano, K.; Fröhlich, R.; Grimme, S.; Glorius, F. Angew. Chem., Int. Ed. 2011, 50, 4983.
[43]	Janssen-Müller, D.; Schedler, M.; Fleige, M.; Daniliuc, C. G.; Glorius, F. Angew. Chem., Int. Ed. 2015, 54, 12492.
[44]	Bandar, J. S.; Ascic, E.; Buchwald, S. L. J. Am. Chem. Soc. 2016, 138, 5821.
[45]	Zhou, Y.; Bander, J. S.; Buchwald, S. L. J. Am. Chem. Soc. 2017, 139, 8126.
[46]	Yang, J.; Rérat, A.; Lim, Y. J.; Gosmini, C.; Yoshikai, N. Angew. Chem., Int. Ed. 2017, 56, 2449.
[47]	Liu, M.; Wang, X.; Guo, Z.; Li, H.; Huang, W.; Xu, H.; Dai, H.-X. Org. Lett. 2021, 23, 6299.
[48]	Jiang, X.; Sheng, F.-T.; Zhang, Y.; Deng, G. Zhu, S. J. Am. Chem. Soc. 2022, 144, 21448.
[49]	Li, W.; Tan, F.; Hao, X.; Wang, G.; Tang, Y.; Liu, X.; Lin, L.; Feng, X. Angew. Chem., Int. Ed. 2015, 54, 1608.
[50]	Chen, D.; Zhang, X.; Qi, W.-Y.; Xu, B.; Xu, M.-H. J. Am. Chem. Soc. 2015, 137, 5268.
[51]	Dou, X.; Lu, Y.; Hayashi, T. Angew. Chem., Int. Ed. 2016, 55, 6739.
[52]	Kong, M.; Tan, Y.; Zhao, X.; Qiao, B.; Tan, C.-H.; Cao, S.; Jiang, Z. J. Am. Chem. Soc. 2021, 143, 4024.
[53]	Zhang, C.; Gao, A. Z.; Nie, X.; Ye, C.-X.; Ivlev, S. I.; Chen, S.; Meggers, E. J. Am. Chem. Soc. 2021, 143, 13393.
[54]	Dai, L.; Zhou, X.; Guo, J.; Dai, X.; Huang, Q.; Lu, Y. Nat. Commun. 2023, 14, 4813.
[55]	Liu, H.-F.; Long, L.; Zhu, Z. Q.; Wu, T.-F.; Zhang, Y.-R.; Pan, H.-P.; Ma, A.-J.; Peng, J.-B.; Wang, Y.-H.; Gao, H.; Zhang, X.-Z. Sci. Adv. 2023, 9, eadg7754.
[56]	Zhou, X.; Huang, Q.; Guo, J.; Dai, L.; Lu, Y. Angew. Chem., Int. Ed. 2023, 62, e202310078.
[57]	Kong, M.; Wang, Z.; Ban, X.; Zhao, X.; Yin, Y.; Zhang, J.; Jiang, Z. Adv. Sci. 2024, 11, 2307773.

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