Progress in Transition Metal Catalyzed C-H Functionalization Directed by Carboxyl Group

doi:10.6023/cjoc201905027

Abstract

The C-H activation assisted by directing groups is an important measure for selective C-H activation at specific positions, and it is also one of the hot spots in the research field of organic chemistry. As an efficient directing group, carboxylic acid has the advantages of low cost, low toxicity, easy modification and using as traceless directing groups. Recent development on C-H functionalization directed by carboxyl group according to different coupling modes is summarized, and the representative reaction mechanism is briefly described. Existing problems with a brief outlook in this field are also presented.

Key words: catalysis, C-H activation, carboxylic acid, traceless directing group, reaction mechanism

Cite this article

Luo Feihua. Progress in Transition Metal Catalyzed C-H Functionalization Directed by Carboxyl Group[J]. Chinese Journal of Organic Chemistry, 2019, 39(11): 3084-3104.

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Fig. & Tab. 29

Scheme 1. Pd catalyzed alkenylation and alkylation of benzoic acid with olefin and its mechanism

Scheme 2. Pd catalyzed coupling of benzoic acid with allene and its mechanism

Scheme 3. Pd catalyzed coupling of benzoic acid with styrene and its mechanism

Scheme 4. Alkylation of benzoic acid with propylene acetate and its mechanism

Scheme 5. Arylation of benzoic acid with halogenated benzene and its possible mechanism

Scheme 6. Arylation of benzoic acid with aryl diazonium and its possible mechanism

Scheme 7. ortho-Directed self-coupling of benzoic acid

Scheme 8. Arylation of benzoic acid with benzene

Scheme 9. Ir catalyzed C—H activation and coupling of benzoic acid with thiophene and its mechanism

Scheme 10. Pd(Ⅱ) catalyzed alkylation of benzoic acid with propylene oxide and its mechanism

Scheme 11. ortho-Alkylation of benzoic acid with propyl alcohol as alkyl source and its mechanism

Scheme 12. Rh(Ⅰ) catalyzed C—H activation and carbonylation of benzoic acid with anhydride and its mechanism

Scheme 13. Amination of benzoic acid with ammonia

Scheme 14. Amidation of benzoic acid with ethyl N-nosyloxycarbamate and its mechanism

Scheme 15. Pt catalyzed intramolecular C—O coupling reactions of chain aliphatic acid

Scheme 16. Pt(Ⅱ) catalyzed C(sp3)—H activation of p-methylbenzoic acid and intramolecular C—O coupling and its mechanism

Scheme 17. Pd(Ⅱ) catalyzed intramolecular C—O coupling reactions of unsaturated aliphatic acid

Scheme 18. Pd(Ⅱ) catalyzed intramolecular C—O coupling reactions of o-phenylbenzoic acid

Scheme 19. Cu(Ⅱ) catalyzed C—H activation of p-phenylbenzoic acid and intramolecular C—O coupling and its mechanism

Scheme 20. Pd(Ⅱ) catalyzed ortho-halogenation of benzoic acid

Scheme 21. Pd(Ⅱ) catalyzed arylation and decarboxylation of benzoic acid with iodobenzene

Scheme 22. meta-Selective arylation of phenol with carboxyl as traceless directing group

Scheme 23. Pd(Ⅱ) catalyzed cross coupling and decarboxylation of benzoic acid and its mechanis

Scheme 24. Ir(Ⅲ) catalyzed coupling and decarboxylation of phenylacetone acid with thiophene and its mechanism

Scheme 25. Alkylation of benzoic acid with alkynes and its mechanism

Scheme 26. Domino coupling reaction and decarboxylation of 2-phenylphenylacetic acid with acrylate and its mechanism

Scheme 27. Alkylation, decarboxylation and arylation of cyclohexadienylformic acid with styrene and its mechanism

Scheme 28. Rh(Ⅲ) catalyzed amidization and decarboxylation of benzoic acid with isocyanate and its mechanism

Scheme 29. Cu(Ⅱ) catalyzed coupling and decarboxylation of benzoic acid with trialkyl boron and its mechanism

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