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Review
. 2019 Mar 18;9(16):8964-8976.
doi: 10.1039/c9ra00929a. eCollection 2019 Mar 15.

Recent developments in decarboxylative cross-coupling reactions between carboxylic acids and N-H compounds

Sattar Arshadi  1 , Saeideh Ebrahimiasl  2   3 , Akram Hosseinian  4 , Aazam Monfared  1 , Esmail Vessally  1
Affiliations
Review

Recent developments in decarboxylative cross-coupling reactions between carboxylic acids and N-H compounds

Sattar Arshadi et al. RSC Adv. .

Abstract

Carboxylic acids and their derivatives are ubiquitous compounds in organic chemistry, and are widely commercially available in a large structural variety. Recently, carboxylic acids have been frequently used as non-toxic and environmentally benign alternatives to traditional organohalide coupling partners in various carbon-carbon and carbon-heteroatom cross-coupling reactions. Along this line, several methods have been reported for the synthesis of nitrogen-containing organic compounds through decarboxylative cross-coupling reactions between carboxylic acids and N-H compounds. This review focuses on recent advances and discoveries on these reactions with special attention on the mechanistic aspects of the reactions.

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Conflict of interest statement

There are no conflicts to declare.

Figures

Fig. 1
Fig. 1. Decarboxylative C–N cross-coupling reactions.
Scheme 1
Scheme 1. (a) I2-catalyzed decarboxylative C–N coupling reactions of primary α-amino acids 1 and 2-aminobenzoketones 2 developed by Wang; (b) synthesis of 2-arylquinazolines 6 through decarboxylative amination of arylacetic acids 4 with 2-aminobenzoketones 5 and NH4OAc.
Scheme 2
Scheme 2. Mechanistic proposal for the formation of quinazoline derivatives 3.
Scheme 3
Scheme 3. Cu(ii)-catalyzed intramolecular decarboxylative C–N coupling reaction of primary aliphatic carboxylic acids 7.
Scheme 4
Scheme 4. Site-selectivity controlled by a directing group in the intramolecular decarboxylative C–N coupling process.
Scheme 5
Scheme 5. Mechanism proposed to explain the formation of cyclic amines 8.
Scheme 6
Scheme 6. Decarboxylative cross-coupling of alkyl carboxylic acids 11 with nitrogen nucleophiles 12 developed by MacMillan research team.
Scheme 7
Scheme 7. Plausible mechanism for reaction in Scheme 6.
Scheme 8
Scheme 8. (a) Cu(ii)-catalyzed decarboxylative C–N coupling reaction between ortho-substituted benzoic acid derivatives 14 and nitrogen nucleophiles 15; (b) mechanism proposed to explain the N-arylated products 16 synthesis.
Scheme 9
Scheme 9. Jia's synthesis of diarylamines 19.
Scheme 10
Scheme 10. Decarboxylative ipso-amination of benzoic acids 20 with aliphatic amines 21 reported by Gooßen.
Scheme 11
Scheme 11. Ru-catalyzed decarboxylative amidation of α-keto acids 23 with amines 24 reported by Lei.
Scheme 12
Scheme 12. Mechanism proposed to explain the secondary amides 25 synthesis.
Scheme 13
Scheme 13. Synthesis of imides 28via Pd-catalyzed decarboxylative amidation of α-keto acids 26 with N-benzylpicolinamides 27.
Scheme 14
Scheme 14. Plausible mechanism for Liu–Wang's synthesis of imides 28.
Scheme 15
Scheme 15. Ag-catalyzed synthesis of secondary amides 31 from α-keto acids 29 and anilines 30via a decarboxylative process.
Scheme 16
Scheme 16. Cu(ii)-catalyzed amidation of propiolic acids 32 with nitrogen nucleophiles 33.
Scheme 17
Scheme 17. Plausible mechanism for the reaction in Scheme 16.
Scheme 18
Scheme 18. Bolm's synthesis of sulfoximidoyl-functionalized alkynes 37.
None
Sattar Arshadi
None
Saeideh Ebrahimiasl
None
Akram Hosseinian
None
Aazam Monfared
None
Esmail Vessally
See this image and copyright information in PMC

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