醇的脱羟官能团化研究进展

doi:10.6023/cjoc202506010

摘要/Abstract

醇作为一种自然界中含量丰富、廉价易得的起始原料, 在有机合成中常被用作合成砌块. 作为醇类化合物的特征性官能团, 羟基是该类化合物的主要反应位点. 因此, 脱羟官能团化反应是醇类化合物的代表性反应之一, 且在构建新的化学键上表现出了巨大的潜力, 近十年来, 该研究领域受到了持续而广泛的关注. 此综述总结了醇类化合物脱羟官能团化的研究进展, 详细阐述了由醇类构建碳杂键和碳碳键的反应方法和机理等.

关键词: 醇, 脱羟官能团化, 脱羟偶联

As naturally abundant and readily available starting materials, alcohols are frequently employed as synthetic building blocks in organic synthesis. The hydroxyl group, which serves as the characteristic functional group of alcohols, is the primary reactive site for these compounds. Consequently, dehydroxylative functionalization reaction is one of the representative transformations of alcohols and has demonstrated significant potential in constructing new chemical bonds. Over the past decade, this research field has received continuous and extensive attention. This review comprehensively summarizes the recent advances in the dehydroxylative functionalization of alcohols, discussing on the reaction methodologies and mechanisms for constructing carbon-heteroatom and carbon-carbon bonds from alcohols.

Key words: alcohols, dehydroxylative functionalizations, dehydroxylative coupling

引用此文

焦燕燕, 王飞格, 肖建, 安孝德. 醇的脱羟官能团化研究进展[J]. 有机化学, 2025, 45(10): 3587-3612.

Yanyan Jiao, Feige Wang, Jian Xiao, Xiaode An. Recent Progress in the Dehydroxylative Functionalizations of Alcohols[J]. Chinese Journal of Organic Chemistry, 2025, 45(10): 3587-3612.

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图/表 41

Scheme 1. Dehydroxylative functionalizations of the alcohols

Scheme 2. Borylation of alcohols catalyzed by metal catalysts

Scheme 3. Transition-metal-free borylation of alcohols

Scheme 4. Electrochemically driven deoxygenative borylation of alcohols

Scheme 5. Dehydroxylative coupling reaction of indoline with alcohols

Scheme 6. Direct azidation of alcohols followed by the click reaction

Scheme 7. Stannylation and silylation reactions of alcohols

Scheme 8. Deoxyphosphonylation of alcohols

Scheme 9. Dehydroxylative thioetherification of alcohols

Scheme 10. Alkynylation of alcohols catalyzed by metal catalyst

Scheme 11. Photocatalytic dehydroxylative alkynylation of alcohols

Scheme 12. Dehydroxylative vinylation reaction of alcohols

Scheme 13. Cross coupling of alcohols and CO2 via photoredox catalysis

Scheme 14. Electrochemical dehydroxylative arylation of alcohols

Scheme 15. Intramolecular dehydroxylative arylation of alcohols via Friedel-Crafts reactions

Scheme 16. Intermolecular dehydroxylative arylation of alcohols with arene

Scheme 17. Metal-free dehydrative coupling of cyclopropane-derived alcohols

Scheme 18. Arylation of alcohols with Grignard reagents

Scheme 19. Arylation of alcohols with aryl halides

Scheme 20. Arylation of alcohols with various aryl electrophiles

Scheme 21. Arylation of alcohols with aryl halides by the merging of photoredox and nickel catalysis

Scheme 22. Arylation of alcohols with aryl halides under the photoredox and nickel catalysis

Scheme 23. Pd(PPh3)4-catalyzed arylation of alcohols with phenylboroxine

Scheme 24. Pd-catalyzed arylation of alcohols with boronic acids

Scheme 25. Ni-catalyzed arylation of alcohols with boronic acids

Scheme 26. Dehydroxylative allylation of alcohols with allytrimethysilane mediated by XtalFluor-E

Scheme 27. Dehydroxylative allylation of alcohols with allytrimethysilane

Scheme 28. Dehydroxylative allylation of alcohols with allytrimethysilane catalyzed by Sc(OTf)3

Scheme 29. Dehydroxylative allylation of alcohols with allytrimethysilane catalyzed by rhenium

Scheme 30. Dehydroxylative allylation of alcohols with allytrimethysilane catalyzed by FeCl3

Scheme 31. Dehydroxylative coupling of alcohols with malonates via C(sp3)—H activation

Scheme 32. Dehydroxylative coupling of alcohols with acetophenones via C(sp3)—H activation

Scheme 33. Dehydroxylative alkylation of alcohols with benzyltrifluoroborates

Scheme 34. Dehydroxylative alkylation of alcohols via C(sp3)—C(sp3) cleavage of cyclopropanol derivatives

Scheme 35. Dehydroxylative alkylation of alcohols via C(sp3)—C(sp3) cleavage of cyclobutanone oxime

Scheme 36. Dehydroxylative alkylation of alcohols with olefin

Scheme 37. Dehydroxylative alkylation of alcohols with olefinic esters and nitriles

Scheme 38. Dehydroxylative alkylation of alcohols with ethyl acrylate and γ,δ-unsaturated oximes

Scheme 39. Ir-catalyzed dehydroxylative alkylation of alcohols with alcohol as alkylation reagent

Scheme 40. Cu-catalyzed dehydroxylative alkylation of alcohols with alcohol as alkylation reagent

Scheme 41. Ru/Ni-catalyzed dehydroxylative alkylation of alcohols with alcohol as alkylation reagent

参考文献 55

[1]	(a) Yang, Q.; Wang, Q.; Yu, Z. Chem. Soc. Rev. 2015, 44, 2305. doi: 10.1039/c4cs00496e pmid: 22778870
	(b) Tang, H.; Luo, J.; Xie, P. Chin. J. Org. Chem. 2019, 39, 2735 (in Chinese). pmid: 22778870
	(唐灏, 骆钧飞, 解攀, 有机化学, 2019, 39, 2735.) doi: 10.6023/cjoc201904011 pmid: 22778870
	(c) Lindsley, C. W. ACS Chem. Neurosci. 2011, 2, 276. doi: 10.1021/cn200050c pmid: 22778870
[2]	(a) Lee, D.-H.; Kwon, K.-H.; Yi, C. S. Science 2011, 333, 1613.
	(b) Jin, J.; MacMillan, D. W. C. Nature 2015, 525, 87.
	(c) Chen, J.; Zhu, G.; Wu, J. Acta Chim. Sin. 2023, 81, 1609.
[3]	(a) Nacsa, E. D.; MacMillan, D. W. C. J. Am. Chem. Soc. 2018, 140, 3322. doi: 10.1021/jacs.7b12768 pmid: 29400958
	(b) Li, Z. J.; Sun, W. X.; Wang, X. X.; Li, L. Y.; Zhang, Y.; Li, C. J. Am. Chem. Soc. 2021, 143, 3536. pmid: 29400958
	(c) Ran, C.-K.; Niu, Y.-N.; Song, L.; Wei, M.-K.; Cao, Y.-F.; Luo, S.-P.; Yu, Y.-M.; Liao, L.-L.; Yu, D.-G. ACS Catal. 2022, 12, 18. pmid: 29400958
[4]	(a) Li, W.-D.; Wu, Y.; Li, S.-J.; Jiang, Y.-Q.; Li, Y.-L.; Lan, Y.; Xia, J.-B. J. Am. Chem. Soc. 2022, 144, 8551.
	(b) Zhang, S.-Q.; Hong, X. Acc. Chem. Res. 2021, 54, 2158.
[5]	(a) Ye, Y.; Chen, H. F.; Sessler, J. L.; Gong, H. G. J. Am. Chem. Soc. 2019, 141, 2, 820. pmid: 21919165
	(b) Yan, X.-B.; Li, C.-L.; Jin, W.-J.; Guo, P.; Shu, X.-Z. Chem. Sci. 2018, 9, 4529. pmid: 21919165
	(c) Qian, X.; Auffrant, A.; Felouat, A; Gosmini, C. Angew. Chem. Int. Ed. 2011, 50, 10402. doi: 10.1002/anie.201104390 pmid: 21919165
[6]	(a) Bandari, C.; Nicholas, K. M. Synthesis 2021, 53, 267.
	(b) Cook, A.; Newman, S. G. Chem. Rev. 2024, 124, 6078.
[7]	Wang, Y.; Xu, J.; Pan, Y.; Wang, Y. Org. Biomol. Chem. 2023, 21, 1121.
[8]	(a) Mandal, T.; Mallick, S.; Islam, M.; Sarkar, S. D. ACS Catal. 2024, 14, 13451.
	(b) Tang, J.; Hu, J.; Zhu, Z. Pu, S. Chin. J. Org. Chem. 2023, 43, 4036 (in Chinese).
	(汤娟, 胡家榆, 祝志强, 蒲守智, 有机化学, 2023, 43, 4036.)
	(c) Yan, B.; Wu, J.; Deng, J.; Chen, D.; Ye, X.; Yao, Q. Chin. J. Org. Chem. 2023, 43, 3055 (in Chinese).
	(鄢伯钰, 吴阶良, 邓金飞, 陈丹, 叶秀深, 姚秋丽, 有机化学, 2023, 43, 3055.)
[9]	(a) Molander, G. A.; Ellis, N. Acc. Chem. Res. 2007, 40, 275. pmid: 31070642
	(b) Smith, K.; Elliott, M. C.; Jones, D. H. J. Org. Chem. 2013, 78, 9526. pmid: 31070642
	(c) Diaz, D. B.; Yudin, A. K. Nat. Chem. 2017, 9, 731. pmid: 31070642
	(d) Mellerup, S. K.; Wang, S. Chem. Soc. Rev. 2019, 48, 3537. doi: 10.1039/c9cs00153k pmid: 31070642
	(e) Fernandes, G. F. S.; Denny, W. A.; Santos, J. L. D. Eur. J. Med. Chem. 2019, 179, 791. pmid: 31070642
	(f) Glasspoole, B. W.; Ghozati, K.; Moir, J. W.; Crudden, C. M. Chem. Commun. 2012, 48, 1230. pmid: 31070642
[10]	Cao, Z.-C.; Luo, F.-X.; Shi, W.-J.; Shi, Z.-J. Org. Chem. Front. 2015, 2, 1505.
[11]	Mao, L. J.; Szabó, K. J.; Marder, T. B. Org. Lett. 2017, 19, 1204.
[12]	Yin, C. Y.; Luo, L.; Zhang, H. Org. Lett. 2023, 25, 1701.
[13]	Guan, W, Y.; Chang, Y, J.; Lin, S. J. Am. Chem. Soc. 2023, 145, 16966.
[14]	Jiang, X.; Tang, W, J.; Xue, D.; Xiao, J, L.; Wang, C. ACS Catal. 2017, 7, 1831.
[15]	Naveen; Babu, S. A.; Aslam, N. A.; Sandhu, A.; Singh, D. K.; Rana, A. Tetrahedron Lett. 2015, 71, 7026.
[16]	Yue, G. L.; Liu, Q. Y.; Wei, J. Y.; Pi, Y. Q.; Qiu, D.; Mo, F. Y. J. Org. Chem. 2023, 88, 2735.
[17]	Bissonnette, N. B.; Bisballe, N.; Tran, A. V.; Rossi-Ashton, J. A.; MacMillan, D. W. C. J. Am. Chem. Soc. 2024, 146, 7942. doi: 10.1021/jacs.4c00557 pmid: 38470101
[18]	Sun, G.; Zhan, S.-P.; Zhao, Y.-F.; Du, X. Y.; Shi, M.-Y.; Li, J.; Yuan, H. L.; Wen, X. A.; Sun, H. B.; Xu, Q.-L. J. Org. Chem. 2024, 89, 1083.
[19]	Hamilton, J. Y.; Sarlah, D.; Carreira, E, M, J. Am. Chem. Soc. 2013, 135, 994. doi: 10.1021/ja311422z pmid: 23256708
[20]	Hamilton, J. Y.; Sarlah, D.; Carreira, E, M., Angew. Chem. 2013, 125, 7680.
[21]	Xie, P. Z.; Sun, Z. L.; Li, S. S.; Zhang, L.; Cai, X. Y.; Fu, W. S.; Yang, X. B.; Liu, Y. N.; Wo, X. Y.; Loh, T.-P. Org. Lett. 2020, 22, 1599.
[22]	He, X.-Y.; Wang, Z.-X. Chem. Commun. 2021, 57, 11988.
[23]	Ma, X. J.; Wang, L. J.; Meng, X. Q.; Li, W. B.; Wang, Q.; Gu, Y. K.; Qiu, L. N. Org. Biomol. Chem. 2023, 21, 6693.
[24]	Xie, H.; Wang, S.; Wang, Y. Q.; Guo, P.; Shu, X.-Z. ACS Catal. 2022, 12, 1018.
[25]	Novaes, L. F. T.; Liu, J. J.; Shen, Y. F.; Lu, L. X.; Meinhardt, J. M.; Lin, S. Chem. Soc. Rev. 2021, 50, 7941. doi: 10.1039/d1cs00223f pmid: 34060564
[26]	Wang, Z. H.; Zhao, X. Q.; Wang, H. Y.; Li, X. Y.; Xu, Z. M.; Ramadoss, V.; Tian, L. F.; Wang, Y. H. Org. Lett. 2022, 24, 7476.
[27]	(a) Friedel, C.; Crafts, J. M. J. Chem. Soc. 1877, 32, 725. pmid: 20485588
	(b) Rueping, M.; Nachtsheim, B. J. Beilstein J. Org. Chem. 2010, 6, 6. doi: 10.3762/bjoc.6.6 pmid: 20485588
[28]	Zheng, Y. Z.; Fang, X.; Deng, W.-H.; Zhao, B.; Liao, R.-Z.; Xie, Y. W. Org. Chem. Front. 2022, 9, 4277.
[29]	Großkopf, J.; Gopatta, C.; Martin, R. T.; Haseloer, A.; MacMillan, D. W. C. Nature 2025, 641, 112.
[30]	Wong, H. N. C.; Hon, M.-Y.; Tse, C.-W.; Yip, Y.-C. Chem. Rev. 1989, 89, 165.
[31]	Yadav, N.; Khan, J.; Tyagi, A.; Singh, S.; Hazra, C. K. J. Org. Chem. 2022, 87, 6886.
[32]	Yu, D.-G.; Wang, X.; Zhu, R.-Y.; Luo, S.; Zhang, X.-B.; Wang, B.-Q.; Wang, L.; Shi, Z.-J. J. Am. Chem. Soc. 2012, 134, 14638.
[33]	Suga, T.; Ukaji. Y. Org. Lett. 2018, 20, 7846.
[34]	Guo, P.; Wang, K.; Jin, W.-J.; Xie, H.; Qi, L. L.; Liu, X.-Y.; Shu, X.-Z. J. Am. Chem. Soc. 2021, 143, 513.
[35]	Dong, Z.; MacMillan, D. W. C. Nature 2021, 598, 451.
[36]	Xiong, W. K.; Kang, T. F.; Li, F.; Liao, H. J.; Yan, Y. G.; Dong, J. Y.; Li, G.; Xue, D. ACS Catal. 2024, 14, 14089.
[37]	Cao, Z.-C.; Yu, D.-G.; Zhu, R.-Y.; Wei, J.-B.; Shi, Z.-J. Chem. Commum. 2015, 51, 2683.
[38]	Toupalas, G.; Thomann, G.; Schlemper, L.; Rivero-Crespo, M. A.; Schmitt, H. L.; Morandi, B. ACS Catal. 2022, 12, 8147.
[39]	Akkarasamiyo, S.; Margalef, J.; Samec, J. S. M. Org. Lett. 2019, 21, 4782. doi: 10.1021/acs.orglett.9b01669 pmid: 31184197
[40]	Lebleu, T.; Paquin, J.-F. Tetrahedron Lett. 2017, 58, 442.
[41]	Šolić, I.; Seankongsuk, P.; Loh, J. K.; Vilaivan, T.; Bates, R. W. Org. Biomol. Chem. 2018, 16, 119.
[42]	Di, Y. J.; Yoshimura, T.; Natio, S.-I.; Kimura, Y.; Kondo, T. ACS Omega 2018, 3, 18885.
[43]	Umeda, R.; Jikyo, T.; Toda, K.; Osaka, I.; Nishiyama, Y. Tetrahedron Lett. 2018, 59, 1121.
[44]	Fujihara, R.; Nakata, K. Eur. J. Org. Chem. 2018, 6566.
[45]	Chen, Z.; Rong, M.-Y.; Nie, J.; Zhu, X.-F.; Shi, B.-F.; Ma, J.-A. Chem. Soc. Rev., 2019, 48, 4921.
[46]	Cao, X. Q.; Zhang, Y. G. Green Chem. 2016, 18, 2638.
[47]	Wagh, K. V.; Bhanage, B. M. ACS Sustainable Chem. Eng. 2016, 4, 445.
[48]	Zhou, P.; Li, Y. Q.; Xu, T. Org. Lett. 2022, 24, 4218. doi: 10.1021/acs.orglett.2c01537 pmid: 35712828
[49]	Zhang, S.-X.; Ding, Y.; Wang, J.-J.; Shen, C. J.; Zhou, X. C.; Chu, X.-Q.; Ma, M. T.; Shen, Z.-L. J. Org. Chem. 2021, 86, 15753.
[50]	He, B.-Q.; Zhao, L.; Zhang, J.; Bao, W.-H.; Yang, M. J.; Wu, X, S, Angew. Chem. Int. Ed. 2025,e202423795.
[51]	Zhao, C.; Ge, Z. L.; Hu, J. H.; Tian, H. J.; Wang, X. M. Cell Rep. 2023, 4, 101474.
[52]	Yao, L. C.; Bao, J. J.; Wang, Y.; Gui, J. H. Org. Lett. 2024, 26, 1243.
[53]	Lu, Z. Y.; Zheng, Q. S.; Yang, S. Q.; Qian. C.; Shen, Y. J.; Tu, T. ACS Catal. 2021, 11, 10796.
[54]	Guo, Z. Q.; Yang, B. R.; Pang, T. F.; Wei, X. H. J. Org. Chem. 2024, 89, 9810.
[55]	Cao, D. W.; Xia, S. M.; Li, L.-J.; Zeng, H. Y.; Li, C.-J. ACS Catal. 2024, 14, 14966.