脱烯丙基反应研究进展

doi:10.6023/cjoc202009031

摘要/Abstract

烯丙基是有机合成中常用的保护基团, 具有引入简单, 在酸/碱性及还原剂等条件下稳定, 在相对温和的条件下选择性地脱保护等特点, 在有机合成特别是药物和天然产物的合成研究中具有重要地位. 近几十年来, 研究者们对各类烯丙基的脱保护方法进行了广泛研究. 按碱及还原剂促进、氧化及自由基过程、路易斯酸促进、碘促进、过渡金属催化及电化学方法等分类, 对脱烯丙基保护方法的研究进展进行了综述.

关键词: 脱烯丙基反应, 碱促进脱烯丙基化, 过渡金属催化脱烯丙基化, 氧化脱烯丙基化, 自由基历程脱烯丙基化, 路易斯酸催化脱烯丙基化, 电化学脱烯丙基化

Allyl groups, as a kind of universal protective groups in organic synthesis, are easily introduced, and stable under acidic, basic and reductive conditions. Moreover, the deallylation may occur efficiently and selectively under mild conditions. Therefore, functional group protection with allyl moiety plays a significant role in organic synthesis, especially in the synthesis of natural products and pharmaceutical industry. In recent decades, various methods of deallylation have been developed. Herein, the comprehensive development on the deallylation reaction with base and reductant, oxidation and free radical, Lewis-acid, iodine, transition metals, and electrochemical methods is reviewed.

Key words: deallylation, base-catalyzed deallylation, transition metal catalyzed deallylation, oxidative deallylation, free radical deallylation, Lewis-acid catalyzed deallylation, electrochemical deallylation

引用此文

王宇, 王泾洋, 吴啸宇, 丁广妮, 张兆国, 谢小敏. 脱烯丙基反应研究进展[J]. 有机化学, 2021, 41(4): 1337-1358.

Yu Wang, Jingyang Wang, Xiaoyu Wu, Guangni Ding, Zhaoguo Zhang, Xiaomin Xie. Advances in Deallylation[J]. Chinese Journal of Organic Chemistry, 2021, 41(4): 1337-1358.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

图/表 28

图式1. 碱促进的异构化脱烯丙基化反应

Scheme 1. Base promoted deallylation reaction via isomerization

图式2. 碱催化的脱烯丙基化合成(R)-Terbutaline

Scheme 2. Synthesis of (R)-Terbutaline via base-catalyzed deallylation

图1. NaBH4促进脱烯丙基化过程中可能形成的六元环过渡态

Figure 1. Possible transition state in deallylation reaction with NaBH4

图式3. 有机锂试剂促进脱烯丙基反应可能反应历程

Scheme 3. Possible reaction pathway of deallylation reaction with tBuLi

图式4. 丁基锂促进的邻位具有甲氧基的芳基烯丙基醚的脱烯丙基化反应

Scheme 4. Deallylation of aryl allyl ethers with ortho-methoxy group promoted by butyl lithium

图式5. SeO2脱烯丙基化反应的反应历程

Scheme 5. Reaction pathway of deallylation with SeO2

图式6. 铬(Ⅲ)催化的脱烯丙基化反应

Scheme 6. Deallylation catalyzed by chromium(Ⅲ)

图式7. DDQ氧化脱烯丙基化的反应机理

Scheme 7. Mechanism of the oxidative deallylation with DDQ

图式8. NBS在光催化条件下脱烯丙基化的反应历程

Scheme 8. Reaction pathway of light-catalyzed deallylation with NBS

图式9. 过硫酸四丁基铵脱烯丙基化的反应机理

Scheme 9. Mechanism of deallylation with (TBA)2S2O8

图式10. 碘化钐促进脱烯丙基化的反应机理

Scheme 10. Mechanism of deallylation with SmI2

图式11. BF3促进的脱烯丙基化反应

Scheme 11. Deallylation promoted by BF3

图式12. 聚乙二醇中碘促进的脱烯丙基可能的反应机理

Scheme 12. Proposed mechanism of iodine-promoted deallylation in PEG

图式13. 低价钛(II)物种还原脱烯丙基化的反应历程

Scheme 13. Reaction pathway of reductive deallylation with Ti(II) species

图式14. 低价钛催化的选择性脱烯丙基化

Scheme 14. Selective deallylation catalyzed by LVT

图式15. 铑催化的异构化脱烯丙基反应

Scheme 15. Rh-catalyzed deallylation via isomerization

图式16. Pd(PPh)4催化胺类化合物脱除烯丙基保护基机理

Scheme 16. Mechanism of Pd(PPh)4 catalyzed deallylation of amines

图式17. Pd(OAc)2/TPPTS催化的选择性脱烯丙基化

Scheme 17. Selective deallylation catalyzed by Pd(OAc)2/ TPPTS

图式18. Pd(PPh3)4/TES催化糖苷类化合物脱烯丙基化反应

Scheme 18. Deallylation of glycosides catalyzed by Pd(PPh3)4/ TES

图式19. [Pd(allyl)Cl]2/GSH催化氨基酸中羧基的脱烯丙基化反应

Scheme 19. Deallylation of carboxyl groups of amino acids catalyzed by [Pd(allyl)Cl]2/GSH

图式20. [(PCy3)2Cl2Ru=CHPh]催化烯丙基胺异构化脱保护机理

Scheme 20. Mechanism of [(PCy3)2Cl2Ru=CHPh] catalyzed deallylation of amines via isomerization

图式21. Grubbs卡宾催化的烯丙基酰胺类化合物脱烯丙基反应

Scheme 21. Deallylation of allyl amides catalyzed by Grubbs carbene

图式22. 生物细胞环境中的钌催化脱烯丙基化反应

Scheme 22. Ruthenium catalyzed deallylation in biological environment

图式23. NiCl2(dppp)/DIBAL催化脱烯丙基过程

Scheme 23. Mechanism of NiCl2(dppp)/DIBAL catalyzed deallylation

图式24. NiCl2(dppe)/tBuMgCl催化三唑和四唑类化合物的脱烯丙基反应可能的机理

Scheme 24. Proposed mechanism of NiCl2(dppe)/tBuMgCl catalyzed deallylation of triazoles and tetrazoles

图式25. NiCl2(dppe)/tBuMgCl催化三唑和四唑类化合物的脱烯丙基脱烯丙基反应可能的烯丙基镍中间体的机理

Scheme 25. Proposed mechanism of NiCl2(dppe)/tBuMgCl catalyzed deallylation of triazoles and tetrazoles via π-allyl nickel

图式26. CoCl2催化脱烯丙基保护机理

Scheme 26. Mechanism of CoCl2 catalyzed deallylation

图式27. Pd (PPh3)4催化的电化学方法脱烯丙酯的烯丙基保护的反应机理

Scheme 27. Mechanism of Pd (PPh3)4 catalyzed electrochemical deallylation of allyl esters

参考文献 104

[1]	Greene, T.W.; Wuts, P.G. M., Protective Groups in Organic Synthesis, 3rd ed., John Wiley & Sons, Inc., New York, 1999.
[2]	(a) Weissman, S.A.; Zewge, D. Tetrahedron 2005, 61,7833.
	(b) Tang, J.-Y.; Liu, H.-X.; Huang, C.-S. Technol. Dev. Chem. Ind. 2016, 45,15. (in Chinese)
	( 唐剑耀, 刘红星, 黄初升, 化学技术与开发, 2016, 45,15.)
	(c) Li, Z.J.; Zhang, S.Q.; Wang, A.B.; Cai, M.S. Acta Chim. Sinica 1998, 56,1128. (in Chinese)
	( 李中军, 张三奇, 王安邦, 蔡孟深, 化学学报, 1998, 56,1128.)
	(d) Zhou, Y.; Zhang, L.R.; Zhang, L.H. Acta Chim. Sinica 2001, 59,1691. (in Chinese)
	( 周英, 张亮仁, 张礼和, 化学学报, 2001, 59,1691.)
	(e) Deng, X.; Liu, W.; Li, C.; Zhang, Z.; Wang, X.; Liu, J. Chin. J. Org. Chem. 2011, 31,75. (in Chinese)
	( 邓喜玲, 刘卫东, 李超, 张志丽, 王孝伟, 刘俊义, 有机化学, 2011, 31,75.)
[3]	(a) Zhang, L.; Wang, Y.; Yu, J.; Zhang, G.; Cai, X.; Wu, Y.; Wang, L. Tetrahedron Lett. 2013, 54,4019.
	(b) Takagi, K.; Fukuda, H.; Shuto, S.; Otaka, A.; Arisawa, M. Adv. Synth. Catal. 2015, 357,2119.
	(c) Bu, X.; Williams, M.; Jo, J.; Koide, K.; Welch, C.J. Chem. Commun. 2017, 53,720.
[4]	Prosser, T.J. J. Am. Chem. Soc. 1961, 83,1701.
[5]	Price, C.C.; Snyder, W.H. J. Am. Chem. Soc. 1961, 83,1773.
[6]	(a) Oltvoort, J.J.; Kloosterman, M.; van Boom, J.H. Recl. Trav. Chim. Pays-Bas 1983, 102,501.
	(b) Guibe, F.; M'Leux, Y.S. Tetrahedron Lett. 1981, 22,3591.
[7]	Gevorgyan, V.; Yamamoto, Y. Tetrahedron Lett. 1995, 36,7765.
[8]	Nicolaou, K.C.; Caulfield, T.J.; Kataoka, H.; Stylianides, N.A. J. Am. Chem. Soc. 1990, 112,3693.
[9]	Gigg, R.; Warren, C.D. J. Chem. Soc. C 1968,1903.
[10]	Halkes, K.M.; Slaghek, T.M.; Vermeer, H.J.; Kamerling, J.P.; Vliegenthart, J.F. G. Tetrahedron Lett. 1995, 36,6137.
[11]	Mereyala, H.B.; Lingannagaru, S.R. Tetrahedron 1997, 53,17501.
[12]	Cunningham, J.; Gigg, R.; Warren, C.D. Tetrahedron Lett. 1964, 5,1191.
[13]	(a) Gigg, J.; Gigg, R. J. Chem. Soc. C 1966,82.
	(b) Smith, A.B.; Rivero, R.A.; Hale, K.J.; Vaccaro, H.A. J. Am. Chem. Soc. 1991, 113,2092.
[14]	Yamada, H.; Harada, T.; Takahashi, T. J. Am. Chem. Soc. 1994, 116,7919.
[15]	Lamberth, C.; Bednarski, M.D. Tetrahedron Lett. 1991, 32,7369.
[16]	Pirrung, F.O. H.; Rutjes, F. P., J.T.; Hiemstra, H.; Speckamp, W.N. Tetrahedron Lett. 1990, 31,5365.
[17]	Effenberger, F.; Jäger, J. J. Org. Chem. 1997, 62,3867.
[18]	Kametani, T.; Huang, S.-P.; Ihara, M.; Fukumoto, K. J. Org. Chem. 1976, 41,2545.
[19]	Thomas, R.M.; Mohan, G.H.; Iyengar, D.S. Tetrahedron Lett. 1997, 38,4721.
[20]	Li, C.B.; Ji, X.J.; Zhang, S.M.; Lu, M.; Zhao, Z.X.; Cui, Y.; Xu, Y.L.; Yang, Q.C.; Zhang, W.Q. Chin. Chem. Lett. 2003, 14,459.
[21]	Pawar, B.V.; Lokhande, P.D. Synth. Commun. 2009, 39,2445.
[22]	Mann, F.G.; Pragnell, M.J. J. Chem. Soc. 1965,4120.
[23]	Bailey, W.F.; England, M.D.; Mealy, M.J.; Thongsornkleeb, C.; Teng, L. Org. Lett. 2000, 2,489. pmid: 10814358
[24]	Sanz, R.; Martinez, A.; Marcos, C.; Fananas, F.J. Synlett 2008,1957.
[25]	Alonso, E.; Ramón, D.J.; Yus, M. Tetrahedron 1997, 53,14355.
[26]	Kariyone, K.; Yazawa, H. Tetrahedron Lett. 1970, 11,2885.
[27]	Choudary, B.M.; Prasad, A.D.; Swapna, V.; Valli, V.L. K.; Bhuma, V. Tetrahedron 1992, 48,953.
[28]	Yadav, J.S.; Chandrasekhar, S.; Sumithra, G.; Kache, R. Tetrahedron Lett. 1996, 37,6603.
[29]	Kumar, P.; Cherian, S.K.; Jain, R.; Show, K. Tetrahedron Lett. 2014, 55,7172.
[30]	Robles, Diaz, R.; Rodriguez Melgarejo, C.; Plaza Lopez-Espinosa, M.T.; Izquierdo Cubero, I. J. Org. Chem. 1994, 59,7928.
[31]	Yang, S.G.; Park, M.Y.; Kim, Y.H. Synlett 2002,492.
[32]	Dahlen, A.; Sundgren, A.; Lahmann, M.; Oscarson, S.; Hilmersson, G. Org. Lett. 2003, 5,4085.
[33]	Escoubet, S.; Gastaldi, S.; Timokhin, V.I.; Ber-trand, M.P.; Siri, D. J. Am. Chem. Soc. 2004, 126,12343.
[34]	Perchyonok, V.T.; Ryan, S.J.; Langford, S.J.; Hearn, M.T.; Tuck, K.L. Synlett 2008,1233.
[35]	Balgotra, S.; Venkateswarlu, V.; Vishwakarma, R.A.; Sawant, S.D. Tetrahedron Lett. 2015, 56,4289.
[36]	Garbers, C.F.; Steenkamp, J.A.; Visagie, H.E. Tetrahedron Lett. 1975, 16,3753.
[37]	Bhatt, M.V.; El-Morey, S.S. Synthesis 1982,1048.
[38]	Akiyama, T.; Hirofuji, H.; Ozaki, S. Tetrahedron Lett. 1991, 32,1321.
[39]	Sakate, S.S.; Kamble, S.B.; Chikate, R.C.; Rode, C.V. New J. Chem. 2017, 41,4943.
[40]	Nagaraju, M.; Krishnaiah, A.; Mereyala, H.B. Synth. Commun. 2007, 37,2467.
[41]	(a) Konda, S.G.; Humne, V.T.; Lokhande, P.D. Green Chem. 2011, 13,2354.
	(b) Humne, V.T.; Hasanzadeh, K.; Lokhande, P.D. Res. Chem. Intermed. 2013, 39,585.
	(c) Humne, V.; Lokahnde, P. Synth. Commun. 2014, 44,929.
[42]	Patil, A.M.; Kamble, D.A.; Lokhande, P.D. ChemistrySelect 2017, 2,8418.
[43]	Satyanarayana, K.; Chidambaram, N.; Chandra-sekaran, S. Synth. Commun. 1989, 19,2159.
[44]	Kadam, S.M.; Nayak, S.K.; Banerji, A. Tetrahedron Lett. 1992, 33,5129.
[45]	Talukdar, S.; Nayak, S.K.; Banerji, A. J. Org. Chem. 1998, 63,4925.
[46]	Lee, J.; Cha, J.K. Tetrahedron Lett. 1996, 37,3663.
[47]	Ohkubo, M.; Mochizuki, S.; Sano, T.; Kawaguchi, Y.; Okamoto, S. Org. Lett. 2007, 9,773.
[48]	Rajakumar, P.; Murali, V. Synth. Commun. 2003, 33,3891.
[49]	Ito, H.; Taguchi, T.; Hanzawa, Y. J. Org. Chem. 1993, 58,774.
[50]	Corey, E.J.; Suggs, J.W. J. Org. Chem. 1973, 38,3224.
[51]	(a) Gent, P.A.; Gigg, R. J. Chem. Soc., hem. Commun. 1974,277.
	(b) Gigg, R. J. Chem. Soc., erkin Trans. 1 1980,738.
[52]	Sundberg, R.J.; Hamilton, G.S.; Laurino, J.P. J. Org. Chem. 1988, 53,976.
[53]	Ziegler, F.E.; Brown, E.G.; Sobolov, S.B. J. Org. Chem. 1990, 55,3691.
[54]	Zacuto, M.J.; Xu, F. J. Org. Chem. 2007, 72,6298.
[55]	Boss, R.; Scheffold, R. Angew. Chem., nt. Ed. 1976, 15,558.
[56]	Mori, M.; Ban, Y. Chem. Pharm. Bull. 1976, 24,1992.
[57]	Bieg, T.; Szeja, W. J. Carbohydr. Chem. 1985, 4,441.
[58]	Nakayama, K.; Uoto, K.; Higashi, K.; Soga, T.; Kusama, T. Chem. Pharm. Bull. 1992, 40,1718.
[59]	Mereyala, H.B.; Guntha, S. Tetrahedron Lett. 1993, 34,6929.
[60]	Honda, M.; Morita, H.; Nagakura, I. J. Org. Chem. 1997, 62,8932.
[61]	(a) Ishizaki, M.; Yamada, M.; Watanabe, S.-I.; Hoshino, O.; Nishitani, K.; Hayashida, M.; Tanaka, A.; Hara, H. Tetrahedron 2004, 60,7973.
	(b) Yamada, M.; Watanabe, S.-I.; Hoshino, O.; Ishizaki, M.; Hayashida, M.; Tanaka, A.; Hara, H. Chem. Pharm. Bull. 2003, 51,1220.
[62]	(a) Hata, G.; Takahashi, K.; Miyake, A. J. Chem. Soc., hem. Commun. 1970,1392.
	(b) Takahashi, K.; Miyake, A.; Hata, G. Bull. Chem. Soc. Jpn. 1972, 45,230.
[63]	Jeffrey, P.D.; McCombie, S.W. J. Org. Chem. 1982, 47,587.
[64]	Kunz, H.; Unverzagt, C. Angew. Chem., nt. Ed. 1984, 23,436.
[65]	Minami, I.; Ohashi, Y.; Shimizu, I.; Tsuji, J. Tetrahedron Lett. 1985, 26,2449.
[66]	(a) Four, P.; Guibe, F. Tetrahedron Lett. 1982, 23,1825.
	(b) Dangles, O.; Guibé, F.; Balavoine, G.; Lavielle, S.; Marquet, A. J. Org. Chem. 1987, 52,4984.
[67]	Roos, E.C.; Bernabe, P.; Hiemstra, H.; Speckamp, W.N.; Kaptein, B.; Boesten, W.H. J. J. Org. Chem. 1995, 60,1733.
[68]	Deziel, R. Tetrahedron Lett. 1987, 28,4371.
[69]	Yamada, T.; Goto, K.; Mitsuda, Y.; Tsuji, J. Tetrahedron Lett. 1987, 28,4557.
[70]	Garro-Helion, F.; Merzouk, A.; Guibé, F. J. Org. Chem. 1993, 58,6109.
[71]	(a) Beugelmans, R.; Bourdet, S.; Bigot, A.; Zhu, J. Tetrahedron Lett. 1994, 35,4349.
	(b) Beugelmans, R.; Neuville, L.; Bois-Choussy, M.; Chastanet, J.; Zhu, J. Tetrahedron Lett. 1995, 36,3129.
[72]	Lemaire-Audoire, S.; Savignac, M.; Genêt, J.P.; Bernard, J.-M. Tetrahedron Lett. 1995, 36,1267.
[73]	(a) Genêt, J.P.; Blart, E.; Savignac, M.; Lemeune, S.; Paris, J.-M. Tetrahedron Lett. 1993, 34,4189.
	(b) Lemaire-Audoire, S.; Savignac, M.; Blart, E.; Pourcelot, G.; Genêt, J.P.; Bernard, J.-M. Tetrahedron Lett. 1994, 35,8783.
	(c) Genêt, J.P.; Blart, E.; Savignac, M.; Lemeune, S.; Lemaire-Audoire, S.; Paris, J.-M.; Bernard, J.-M. Tetrahedron 1994, 50,497.
	(d) Lemaire-Audoire, S.; Savignac, M.; Pourcelot, G.; Genet, J.-P.; Bernard, J.-M. J. Mol. Catal. A: Chem. 1997, 116,247.
[74]	Seki, M.; Kondo, K.; Kuroda, T.; Yamanaka, T.; Iwasaki, T. Synlett 1995,609.
[75]	Murakami, H.; Minami, T.; Ozawa, F. J. Org. Chem. 2004, 69,4482. pmid: 15202905
[76]	Mora, G.; Piechaczyk, O.; Le Goff, X.F.; Le Floch, P. Organometallics 2008, 27,2565.
[77]	Mao, Y.; Liu, Y.; Hu, Y.; Wang, L.; Zhang, S.; Wang, W. ACS Catal. 2018, 8,3016.
[78]	Enugala, R.; Carvalho, L.C. R.; Marques, M.M. B. Synlett 2010,2711.
[79]	Martínez-Calvo, M.; Couceiro, J.R.; Destito, P.; Rodríguez, J.; Mosquera, J.; Mascareñas, J.L. ACS Catal. 2018,8.
[80]	Garner, A.L.; Song, F.; Koide, K. J. Am. Chem. Soc. 2009, 131,5163.
[81]	Nieberding, M.; Tracey, M.P.; Koide, K. ACS Sens. 2017, 2,1737. pmid: 29058887
[82]	Jbara, M.; Eid, E.; Brik, A. Org. Biomol. Chem. 2018, 16,4061. pmid: 29766191
[83]	Alcaide, B.; Almendros, P.; Alonso, J.M. Chem.-Eur. J. 2003, 9,5793. pmid: 14673850
[84]	Alcaide, B.; Almendros, P.; Alonso, J.M. Chem.-Eur. J. 2006, 12,2874. pmid: 16419144
[85]	Tanaka, S.; Saburi, H.; Ishibashi, Y.; Kitamura, M. Org. Lett. 2004, 6,1873. pmid: 15151436
[86]	Tanaka, S.; Saburi, H.; Kitamura, M. Adv. Synth. Catal. 2006, 348,375.
[87]	Tanaka, S.; Saburi, H.; Murase, T.; Yoshimura, M.; Kitamura, M. J. Org. Chem. 2006, 71,4682.
[88]	Cadierno, V.; Garcia-Garrido, S.E.; Gimeno, J.; Nebra, N. Chem. Commun. 2005,4086.
[89]	Kamijo, S.; Huo, Z.; Jin, T.; Kanazawa, C.; Yamamoto, Y. J. Org. Chem. 2005, 70,6389.
[90]	Kajihara, K.; Arisawa, M.; Shuto, S. J. Org. Chem. 2008, 73,9494. pmid: 18980332
[91]	Sasmal, P.K.; Carregal-Romero, S.; Parak, W.J.; Meggers, E. Organometallics 2012, 31,5968.
[92]	Rodriguez, J.G.; Canoira, L. React. Kinet. Catal. Lett. 1989, 38,351.
[93]	Chouhan, M.; Kumar, K.; Sharma, R.; Grover, V.; Nair, V.A. Tetrahedron Lett. 2013, 54,4540.
[94]	Taniguchi, T.; Ogasawara, K. Angew. Chem., nt. Ed. 1998, 37,1136.
[95]	Taniguchi, T.; Ogasawara, K. Tetrahedron Lett. 1998, 39,4679.
[96]	Kim, S.; Jo, J.; Lee, D. Org. Lett. 2016, 18,4530. doi: 10.1021/acs.orglett.6b02140 pmid: 27560493
[97]	Gaertner, D.; Konnerth, H.; von Wangelin, A.J. Catal. Sci. Technol. 2013, 3,2541.
[98]	Iqbal, J.; Srivastava, R.R. Tetrahedron 1991, 47,3155.
[99]	Giedyk, M.; Turkowska, J.; Lepak, S.; Mar-culewicz, M.; Proinsias, K.O.; Gryko, D. Org. Lett. 2017, 19,2670. doi: 10.1021/acs.orglett.7b01012
[100]	Hemming, D.S.; Talbot, E.P.; Steel, P.G. Tetrahedron Lett. 2017, 58,17. doi: 10.1016/j.tetlet.2016.11.084
[101]	Torii, S.; Tanaka, H.; Katoh, T.; Morisaki, K. Tetrahedron Lett. 1984, 25,3207. doi: 10.1016/S0040-4039(01)91010-X
[102]	Espanet, B.; Duñach, E.; Périchon, J. Tetrahedron Lett. 1992, 33,2485.
[103]	Olivero, S.; Duñach, E. J. Chem. Soc., hem. Commun. 1995,2497.
[104]	Yasuhara, A.; Kasano, A.; Sakamoto, T. J. Org. Chem. 1999, 64,4211.