巢式-碳硼烷硼氢键官能化反应研究进展

doi:10.6023/cjoc202307006

摘要/Abstract

巢式-碳硼烷是医学、材料科学和有机金属/配位化学等领域中多功能的重要砌块. 近年来, 巢式-碳硼烷的硼氢键直接活化及官能化反应受到了广泛关注. 由于碳硼烷通常含有十个化学环境相似的硼氢键, 因此区域选择控制一直是碳硼烷硼氢键活化的一个长期挑战. 近年来, 巢式-碳硼烷开口平面上的硼氢键官能化取得了重大进展, 而非开口球面上的硼氢键选择性活化依然具有挑战性. 总结了巢式-碳硼烷的区域选择性硼氢键官能化反应的研究进展, 从开口面和非开口面硼氢键活化两个角度进行梳理.

关键词: 碳硼烷, 硼氢键活化, 区域选择性, 官能化, 导向基团

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

引用此文

付雅彤, 孙超凡, 张丹, 金成国, 陆居有. 巢式-碳硼烷硼氢键官能化反应研究进展[J]. 有机化学, 2024, 44(2): 438-447.

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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图/表 29

图式1. 巢式-碳硼烷硼氢键官能化的策略

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

图式2. 巢式-碳硼烷的卤化

Scheme 2. Halogenation of nido-carborane

图式3. 巢式-碳硼烷烷基化、质子化及重排反应

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

图式4. 巢式-碳硼烷与亲电试剂反应

Scheme 4. Reactions of nido-carborane with electrophiles

图式5. 巢式-碳硼烷与硫代乙酰胺反应

Scheme 5. Reaction of nido-carborane with thioacetamide

图式6. 硼硫键偶联工艺改进

Scheme 6. Improvement of B—S bond coupling

图式7. 甲基取代异构体

Scheme 7. Methyl substituted isomers

图式8. 巢式-碳硼烷的硼氮和硼硫偶联

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

图式9. 巢式-碳硼烷硼氮偶联

Scheme 9. B—N Coupling of nido-carborane

图式10. 氯化汞氧化制备巢式-碳硼烷腈

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

图式11. 巢式-碳硼烷与胺的反应

Scheme 11. Reaction of nido-carborane with amines

图式12. DDQ氧化的硼氮偶联

Scheme 12. B—N coupling via DDQ oxidation

图式13. DDQ氧化的反应机理

Scheme 13. Reaction mechanism of DDQ oxidation

图式14. 电氧化偶联

Scheme 14. Electrooxidation coupling

图式15. 氘代实验

Scheme 15. Deuterium experiment

图式16. 电氧化偶联反应机理

Scheme 16. Reaction mechanism of electrooxidation coupling

图式17. 电化学氧化的硼氮偶联

Scheme 17. Electrooxidation B—N coupling

图式18. 电化学氧化硼氮偶联的反应机理

Scheme 18. Reaction mechanism of electrooxidation B—N coupling

图式19. 光氧化硼氢键活化机理

Scheme 19. Mechanism of photooxidation B—H bond activation

图式20. 钯催化分子内硼氧偶联的机理

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

图式21. 铱催化合成巢式-碳硼烷

Scheme 21. Synthesis of nido-carborane via iridium catalysis

图式22. 巢式-碳硼烷的硼碳偶联

Scheme 22. B—C Coupling of nido-carborane

图式23. 巢式-碳硼烷与炔烃的偶联

Scheme 23. Coupling of nido-carborane with alkynes

图式24. 巢式-碳硼烷与炔烃反应机理

Scheme 24. Reaction mechanism of nido-carborane with alkynes

图式25. 巢式-碳硼烷B(11)—H膦化反应

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

图式26. 脱硼实验

Scheme 26. Deboronization experiments

图式27. 巢式-碳硼烷B(11)-膦化反应机理

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

图式28. 巢式-碳硼烷的B(6)—H膦化

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

图式29. 巢式-碳硼烷B(6)-膦化反应机理

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

参考文献 35

[1]	Wiesboeck, R. A.; Hawthorne, M. F. J. Am. Chem. Soc. 1964, 86, 1642. doi: 10.1021/ja01062a042
[2]	(a) Batsanov, A. S.; Clegg, W.; Copley, R. C. B.; Fox, M. A.; Gill, W. R.; Grimditch, R. S.; Hibbert, T. G.; Howard, J. A. K.; Macbride, J. A. H.; Wade, K. Polyhedro. 2006, 25, 300. doi: 10.1016/j.poly.2005.06.046
	(b) Powell, C. L.; Schulze, M.; Black, S. J.; Thompson, A. S.; Threadgill, M. D. Tetrahedron Lett. 2007, 48, 1251. doi: 10.1016/j.tetlet.2006.12.034
	(c) Prokhorov, A. M.; Kozhevnikov, D. N.; Rusino, V. L. Organometallic. 2006, 25, 2972. doi: 10.1021/om051058v
[3]	Ristori, S.; Salvati, A.; Martini, G. J. Am. Chem. Soc. 2007, 129, 2728. pmid: 17298062
[4]	Barth, R. F.; Mi, P.; Yang, W.-L. Cancer Commun. 2018, 38, 1.
[5]	Hawthorne, M. F.; Young, D. C.; Wegner, P. A. J. Am. Chem. Soc. 1965, 87, 1818. doi: 10.1021/ja01086a053
[6]	Issa, F.; Kassiou, M.; Rendina, L. M. Chem. Rev. 2011, 111, 5701. doi: 10.1021/cr2000866
[7]	(a) Slough, W. J.; Kandalam, A. K.; Pandey, R. J. Chem. Phys. 2010, 132, 104304. doi: 10.1063/1.3336404
	(b) Chuiko, S. V.; Sokolovskii, F. S. Russ. J. Phys. Chem. . 2009, 28, 49.
	(c) Nechai, G. V.; Sokolovskii, F. S.; Chuiko, S. V. Russ. J. Phys. Chem. . 2009, 28, 46.
[8]	Kang, H. C.; Lee, S. S.; Knobler, C. B. Inorg. Chem. 1991, 30, 2024. doi: 10.1021/ic00009a015
[9]	(a) Mizusawa, E. A.; Thompson, M. R.; Hawthorne, M. F. Inorg. Chem. 1985, 24, 1911. doi: 10.1021/ic00206a043
	(b) Pak, R. H.; Kane, R. R.; Knobler, C. B. Inorg. Chem. 1994, 33, 5355. doi: 10.1021/ic00101a031
	(c) Santos, E. C.; Pinkerton, A. B.; Kinkead, S. A. Polyhedro. 2000, 19, 1777. doi: 10.1016/S0277-5387(00)00461-7
	(d) Rudakov, D. A.; Potkin, V. I.; Dikusar, E. A. Russ. Chem. Bull. 2007, 56, 922. doi: 10.1007/s11172-007-0140-y
[10]	Rudakova, D. A.; Shirokiia, V. L.; Potkin, V. I. Russ. J. Electrochem. 2006, 42, 280. doi: 10.1134/S102319350603013X
[11]	Fox, M. A.; Hughes, A. K.; Malget, J. M. J. Chem. Soc.. Dalton Trans. 2002, 3505.
[12]	Tutusau, O.; Teixidor, F.; Nuez, R. J. Organomet. Chem. 2002, 657, 247. doi: 10.1016/S0022-328X(02)01541-3
[13]	Frank, R.; Grell, T.; Hiller, M.; Hawkins, H. E. Dalton Trans. 2012, 41, 6155. doi: 10.1039/c2dt12501c pmid: 22499251
[14]	Zakharkin, L. I.; Grandberg, N. V.; Antonovich, V. A. Izv. Akad. Nauk SSSR. Ser. Khim. 1976, 1830.
[15]	Zakharkin, L. I.; Ol’shevskaya, V. A.; Zhigareva, G. G.; Antonovich, V. A.; Petrovskii, P. V.; Yanovskii, A. I.; Polyakov, A. V.; Struchkov, Y. T. Metalloorg. Khim. 1989, 2, 1274.
[16]	Frank, R.; Auer, H.; Hawkins, E. J. Organomet. Chem. 2013, 747, 217. doi: 10.1016/j.jorganchem.2013.04.031
[17]	Vinogradov, M. M.; Nelyubina, Y. V.; Aliyeu, T. M. Polyhedro. 2022, 214, 115654. doi: 10.1016/j.poly.2022.115654
[18]	Kang, H. C.; Lee, S. S.; Knobler, C. B. Inorg. Chem. 1991, 30, 2024. doi: 10.1021/ic00009a015
[19]	Rudakov, D. A.; Potkin, V. I.; Dikusar, E. A. Russ. Chem. Bull. 2007, 56, 922. doi: 10.1007/s11172-007-0140-y
[20]	Meshcheryakov, V. I.; Kitaev, P. S.; Lyssenko, K. A. J. Organomet. Chem. 2005, 690, 4745. doi: 10.1016/j.jorganchem.2005.07.067
[21]	Jasper, S. A.; Mattern, J.; Huffman, J. C. Polyhedro. 2007, 26, 3793. doi: 10.1016/j.poly.2007.04.025
[22]	Frank, R.; Auer, H.; Hawkins, E. J. Organomet. Chem. 2013, 747, 217. doi: 10.1016/j.jorganchem.2013.04.031
[23]	Stogniyi, M. Y.; Erokhinai, S. A.; Suponitskyi, K. Y. New J. Chem. 2018, 42, 17958. doi: 10.1039/C8NJ04192J
[24]	Timofeevs, V.; Hidkova, O. B.; Prikaznova, E. A. J. Organomet. Chem. 2014, 757, 21. doi: 10.1016/j.jorganchem.2014.01.026
[25]	Yang, Z.-M; Zhao, W.-J; Liu, W.; Wei, X.; Chen, M.; Zhang, X.; Zhang, X.-L.; Liang, Y.; Lu, C.-S.; Yan, H. Angew. Chem. 2019, 131, 12012. doi: 10.1002/ange.v131.34
[26]	Chen, M.; Zhao, D.; Xu, J.; Li, C.-X.; Lu, C.-S.; Yan, H. Angew. Chem.. Int. Ed. 2021, 60, 7838. doi: 10.1002/anie.v60.14
[27]	Yang, L.; Jei, B.-B.; Scheremetjew, A.; Kuniyil, R.; Ackermann, L. Angew. Chem.. Int. Ed. 2020, 60, 1482. doi: 10.1002/anie.v60.3
[28]	Huang, R.-H.; Zhao, W.-J.; Xu, S.-W.; Xu, J.-K.; Li, C.-X.; Lu, C.-S.; Yan, H. Chem. Commun. 2021, 57, 8580. doi: 10.1039/D1CC03326C
[29]	Mirabelli, M. G. L.; Sneddon, L. G. J. Am. Chem. Soc. 1988, 110, 449. doi: 10.1021/ja00210a023
[30]	Zhang, C.-Y.; Cao, K.; Xu, T.-T.; Wu, J.; Jiang, L.-H.; Yang, J.-X. Chem. Commun. 2019, 55, 830. doi: 10.1039/C8CC07728B
[31]	Han, G.; Baek, Y.; Lee, K. Org. Lett. 2021, 23, 416. doi: 10.1021/acs.orglett.0c03927 pmid: 33377789
[32]	Sun, F.-X.; Tan, S.-M.; Cao, H.-J.; Xu, J.-K.; Bregadze, V. I.; Tu, D. S.; Lu, C.-S.; Yan, H. Angew. Chem.. Int. Ed. 2022, 61, e202207125.
[33]	Sun, F.-X; Tan, S.-M; Cao, H.-J.; Lu, C.-S.; Tu, D.-S.; Poater, J.; Solà, J.; Yan, H. J. Am. Chem. Soc. 2023, 145, 3577. doi: 10.1021/jacs.2c12526
[34]	Yang, Z.-Y.; Sun, C.-F.; Wei, X.; Lu, J.; Lu, J.-Y. ChemCatChe. 2022, 14, 1867.
[35]	Sun, C.-F.; Lu, J.-Y.; Lu, J. Inorg. Chem. 2022, 61, 9623. doi: 10.1021/acs.inorgchem.2c00993