Research Progress of Amino Acids as Transient Directing Groups in C—H Bond Activation Reactions

doi:10.6023/cjoc202212012

Abstract

In recent years, the transient directing group (TDG)-based strategy of C—H activation has attracted significant attention. Compared with the typical C—H activation reactions, TDG-assisted C—H activation does not require external pre-installation and post-removal steps of directing groups, which significantly improve the atom and step economy. Amino acid-based TDGs for C—H activation have achieved significant successes among the known TDGs. Amino acids have the advantages including low cost, widely existing and diverse structures. The site selectivity of C—H activation can be controlled by using α- or β-amino acids. By using the inherent chirality of amino acids, the stereo-selectivity of reactions can be realized. The research progress of transition-metal-catalyzed C—H bond activation and functionalization with amino acids as TDGs in recent years is summarized, which is classified according to the type of amino acids for C—H activation reactions of various substrates. Finally, the limitations of previous works and perspectives on this cutting-edge area are also described.

Key words: transient directing group, amino acid, C—H activation, transition metal

Cite this article

Sifan Dong, Haolong Li, Yuan Qin, Shiming Fan, Shouxin Liu. Research Progress of Amino Acids as Transient Directing Groups in C—H Bond Activation Reactions[J]. Chinese Journal of Organic Chemistry, 2023, 43(7): 2351-2367.

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Fig. & Tab. 40

Scheme 1. Directing strategies for traditional and transient directing groups

Figure 1. Amino acid directing groups

Scheme 2. Palladium-catalyzed benzylic C(sp3)—H arylation of aromatic aldehydes and β-C(sp3)—H arylation of aliphatic ketones

Scheme 3. Palladium-catalyzed synthesis of polycyclic aromatic hydrocarbons

Scheme 4. Palladium-catalyzed ortho-C(sp2)—H arylation of aromatic aldehydes

Scheme 5. Proposed catalytic mechanism of palladium-catalyzed ortho-C(sp2)—H arylation of aromatic ketones

Scheme 6. Palladium-catalyzed regioselective C(4) functionalization of indole and azaindole

Scheme 7. Proposed catalytic mechanism of palladium-catalyzed arylation of indole at C(4)

Scheme 8. Palladium-catalyzed ortho-C(sp2)—H arylation of aromatic aldehydes

Scheme 9. Palladium-catalyzed ortho-C(sp2)—H arylation of aromatic aldehydes

Scheme 10. Proposed catalytic mechanism of palladium-catalyzed ortho-C(sp2)—H arylation of aromatic aldehyde

Scheme 11. Palladium-catalyzed β-C(sp3)—H arylation of aliphatic aldehydes

Scheme 12. Palladium-catalyzed benzylic C(sp3)—H arylation of aromatic aldehydes

Scheme 13. Palladium-catalyzed β-C(sp3)—H arylation of aliphatic aldehydes

Scheme 14. Palladium-catalyzed γ-C(sp3)—H arylation of aliphatic aldehydes

Scheme 15. Palladium-catalyzed olefin benzaldehyde C(alkenyl)—H alkenylation

Scheme 16. Proposed catalytic mechanism of palladium-catalyzed C(alkenyl)—H alkenylation

Scheme 17. Palladium-catalyzed C(sp2)—H deuteration of aromatic aldehydes

Scheme 18. Proposed catalytic mechanism of palladium-catalyzed C(sp2)—H deuteration of aromatic aldehydes

Figure 2. [6,5] and [5,6]-bicyclic palladium intermediates

Scheme 19. Palladium-catalyzed β-C(sp3)—H arylation of aliphatic aldehydes

Scheme 20. Proposed catalytic cycle of palladium-catalyzed β-C(sp3)—H arylation of aliphatic aldehydes

Scheme 21. Palladium-catalyzed β-C—H arylation of saturated aldehydes

Scheme 22. Proposed catalytic cycle of palladium-catalyzed β-C—H arylation of saturated aldehydes

Scheme 23. Rhodium(III)-catalyzed intramolecular olefin hydroarylation of aromatic aldehydes

Scheme 24. Proposed catalytic cycle of rhodium(III)-catalyzed intramolecular olefin hydroarylation of aromatic aldehydes

Scheme 25. Ketone-catalyzed ortho-C(sp2)—H sulfonylation of aromatic aldehydes

Scheme 26. Proposed catalytic cycle of ketone-catalyzed ortho-C(sp2)—H sulfonylation of aromatic aldehydes

Scheme 27. Palladium-catalyzed β-C(sp3)—H arylation of aliphatic ketones

Scheme 28. Palladium-catalyzed synthesis of fluorenones from benzaldehydes and aryl iodides

Scheme 29. Proposed catalytic cycle of palladium-catalyzed synthesis of fluorenones from benzaldehydes and aryl iodides

Figure 3. [5,5] or [5,6]-bicyclic palladium intermediate

Scheme 30. Palladium-catalyzed benzylic C(sp3)—H arylation of aromatic aldehydes

Scheme 31. Palladium-catalyzed benzylic C(sp3)—H fluoridation of aromatic aldehydes

Scheme 32. Palladium-catalyzed atroposelective C(sp2)—H olefination of biaryl aldehydes

Scheme 33. Palladium-catalyzed atroposelective C(sp2)—H alkynylation of biaryl aldehydes

Scheme 34. Palladium-catalyzed enantioselective C(sp2)—H arylation of ferrocenyl ketones

Scheme 35. Palladium-catalyzed atroposelective C(sp2)—H arylation of biaryl aldehydes

Scheme 36. Palladium-catalyzed asymmetric reductive Heck arylation of alkenyl benzaldehydes and proposed mechanism

Scheme 37. Palladium-catalyzed β-C(sp3)—H arylation of aliphatic ketones

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