Recent Progress in B—H Bond Functionalization of nido-Carboranes

doi:10.6023/cjoc202307006

Abstract

nido-Carboranes are versatile building blocks in medicine, materials science, and organometallic/coordination chemistry. Recently, direct B—H activation and functionalization of nido-carboranes have received much attention. Achieving regioselectivity in polyhedral cage B—H activation among ten chemically similar B—H vertices is a long-standing challenge in carborane chemistry. In this context, the activation of exo-cage B—H vertices on the open C₂B₃ pentagonal plane of nido-carboranes has been extensively studied. However, few direct activation reactions of B—H vertices that are located on the closed polyhedral sphere in nido-carborane have been reported. The recent progress on the regioselective B—H bond functionalization reaction of nido-carboranes is summarized. This topic is categorized into open plane exo-B—H activation and polyhedral sphere B—H activation.

Key words: carboranes, B—H bond activation, regioselectivity, functionalization, directing group

Cite this article

Yatong Fu, Chaofan Sun, Dan Zhang, Chengguo Jin, Juyou Lu. Recent Progress in B—H Bond Functionalization of nido-Carboranes[J]. Chinese Journal of Organic Chemistry, 2024, 44(2): 438-447.

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Fig. & Tab. 29

Scheme 1. General strategies for B—H bond functionalization of nido-carboranes

Scheme 2. Halogenation of nido-carborane

Scheme 3. Alkylation, protonation and rearrangement reactions of nido-carborane

Scheme 4. Reactions of nido-carborane with electrophiles

Scheme 5. Reaction of nido-carborane with thioacetamide

Scheme 6. Improvement of B—S bond coupling

Scheme 7. Methyl substituted isomers

Scheme 8. B—N and B—S coupling of nido-carborane

Scheme 9. B—N Coupling of nido-carborane

Scheme 10. Preparation of nido-carborane nitriles via mercuric chloride oxidation

Scheme 11. Reaction of nido-carborane with amines

Scheme 12. B—N coupling via DDQ oxidation

Scheme 13. Reaction mechanism of DDQ oxidation

Scheme 14. Electrooxidation coupling

Scheme 15. Deuterium experiment

Scheme 16. Reaction mechanism of electrooxidation coupling

Scheme 17. Electrooxidation B—N coupling

Scheme 18. Reaction mechanism of electrooxidation B—N coupling

Scheme 19. Mechanism of photooxidation B—H bond activation

Scheme 20. Mechanism of Pd-catalyzed intramolecular B—O coupling

Scheme 21. Synthesis of nido-carborane via iridium catalysis

Scheme 22. B—C Coupling of nido-carborane

Scheme 23. Coupling of nido-carborane with alkynes

Scheme 24. Reaction mechanism of nido-carborane with alkynes

Scheme 25. B(11)—H phosphylation of nido-carborane

Scheme 26. Deboronization experiments

Scheme 27. Reaction mechanism of B(11)-phosphylation of nido-carborane

Scheme 28. B(6)—H phosphylation of nido-carborane

Scheme 29. Reaction mechanism of B(6)-phosphylation of nido-carborane

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