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Review
. 2019 May 31;9(30):17101-17118.
doi: 10.1039/c9ra01941c. eCollection 2019 May 29.

Cross-dehydrogenative coupling reactions between arenes (C-H) and carboxylic acids (O-H): a straightforward and environmentally benign access to O-aryl esters

Sattar Arshadi  1 , Alireza Banaei  1 , Aazam Monfared  1 , Saeideh Ebrahimiasl  2   3 , Akram Hosseinian  4
Affiliations
Review

Cross-dehydrogenative coupling reactions between arenes (C-H) and carboxylic acids (O-H): a straightforward and environmentally benign access to O-aryl esters

Sattar Arshadi et al. RSC Adv. .

Abstract

Transition-metal catalyzed cross-dehydrogenative-coupling reactions encompass highly versatile and atom economical methods for the construction of various carbon-carbon and carbon-heteroatom bonds by combining two C(X)-H (X = heteroatom) bonds. Along this line, direct acyloxylation of C-H bonds with carboxylic acids has emerged as a powerful and green approach for the synthesis of structurally diverse esters. In this focus-review we will describe recent progress in direct esterification of aromatic C-H bonds with special emphasis on the mechanistic features of the reactions. Literature has been surveyed until the end of February 2019.

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Conflict of interest statement

There are no conflicts to declare.

Figures

Fig. 1
Fig. 1. Some ester-containing commercialized drugs.
Fig. 2
Fig. 2. Direct esterification of aromatic C–H bonds with carboxylic acids.
Scheme 1
Scheme 1. Rh-catalyzed direct benzoxylation of 2-arylpyridines 1 with benzoic acids 2.
Scheme 2
Scheme 2. Mechanistic proposal for the formation of ortho-acyloxylated 2-arylpyridines 3.
Scheme 3
Scheme 3. Some reported examples on the Rh-catalyzed ortho-selective acyloxylation of arene substrates 4 bearing coordinating directing groups with aliphatic carboxylic acids 5 reported by Xu and Li.
Scheme 4
Scheme 4. Ru-catalyzed synthesis of ortho-benzoxylated acetanilides 9 from acetanilides 7 and benzoic acids 8.
Scheme 5
Scheme 5. Cross-dehydrogenative coupling of N-methyl benzamides 10 with aromatic carboxylic acids 11 catalyzed by [{RuCl2(p-cymene)}2].
Scheme 6
Scheme 6. Suggested mechanism for the formation of ortho-benzoxylated N-alkyl benzamides 12.
Scheme 7
Scheme 7. (a) Ackermann's synthesis of ortho-benzoxylated sulfoximines 15; (b) plausible mechanism for the formation of ortho-benzoxylated sulfoximines 15.
Scheme 8
Scheme 8. Ru-catalyzed ortho-directed aromatic amines 16 with carboxylic acids 17.
Scheme 9
Scheme 9. Ru-catalyzed site-selective acyloxylation of indolines 19 with carboxylic acids 20.
Scheme 10
Scheme 10. ortho-Selective acyloxylation of azoarenes 22 with carboxylic acids 23 reported by Kianmehr.
Scheme 11
Scheme 11. Pd-catalyzed cross-dehydrogenative coupling of O-methyl aryloximes 25 with carboxylic acids 26.
Scheme 12
Scheme 12. Coupling of 2-arylpyridines 28 with carboxylic acids 29 catalyzed by Pd(OAc)2.
Scheme 13
Scheme 13. Plausible mechanism for the Pd-catalyzed acyloxylation of 2-arylpyridines 28 with carboxylic acids 29.
Scheme 14
Scheme 14. Synthesis of lactones 32 from the corresponding 2-aryl carboxylic acids 31.
Scheme 15
Scheme 15. Pd-catalyzed ortho-acyloxylation of 2-substituted 1,2,3-triazoles 33 with different carboxylic acids 34.
Scheme 16
Scheme 16. (a) Pd-catalyzed dehydrogenative cross-coupling of simple benzene with carboxylic acids 36; (b) Pd-catalyzed para-benzoxylation of anisole derivatives 38 with simple benzoic acid.
Scheme 17
Scheme 17. Proposed mechanism for the reaction in Scheme 16a.
Scheme 18
Scheme 18. Liao-Ji's synthesis of mono-acyloxylated 4-aryl-thiazoles 42.
Scheme 19
Scheme 19. (a) Pd-catalyzed direct esterification of 2-substituted indoles 43 with carboxylic acids 44; (b) Pd-catalyzed direct esterification of 2,3-unsubstituted indoles 46 with carboxylic acids 47.
Scheme 20
Scheme 20. Mechanistic explanation for the synthesis of acyloxylated indoles 48.
Scheme 21
Scheme 21. Co-catalyzed cross-dehydrogenative coupling of N-aryl-2-pyridylcarboxamides 49 with carboxylic acids 50.
Scheme 22
Scheme 22. Possible mechanism for the Co-catalyzed oxidative coupling between an arene 49 and carboxylic acid 50.
Scheme 23
Scheme 23. Coupling of N-(quinolin-8-yl)benzamides 52 with carboxylic acids 53 catalyzed by Co(acac)2.
Scheme 24
Scheme 24. Cu-catalyzed intramolecular C–H oxygenation reaction of 2-arylbenzoic acid derivatives 55.
Scheme 25
Scheme 25. Zhang's synthesis of mono-acyloxylated of N-(quinolin-8-yl)benzamides 59.
Scheme 26
Scheme 26. (a) Cu-catalyzed C–H acyloxylation of 2-arylpyridines 60 with carboxylic acids 61; (b) Cu-catalyzed C–H acyloxylation of indolines 63 with carboxylic acids 64.
Scheme 27
Scheme 27. Au-catalyzed oxidative acyloxylation of simple arenes 66.
Scheme 28
Scheme 28. Proposed mechanism for the reaction in Scheme 27.
Scheme 29
Scheme 29. Xu's synthesis of lactones 70.
Scheme 30
Scheme 30. Ag-catalyzed intramolecular C–O cross-coupling of biaryl-2-carboxylic acids 71 through C–H acyloxylation.
None
Sattar Arshadi
None
Alireza Banaei
None
Aazam Monfared
None
Saeideh Ebrahimiasl
None
Akram Hosseinian
See this image and copyright information in PMC

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