Advances in Deallylation

doi:10.6023/cjoc202009031

Abstract

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

Cite this article

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.

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Fig. & Tab. 28

Scheme 1. Base promoted deallylation reaction via isomerization

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

Figure 1. Possible transition state in deallylation reaction with NaBH4

Scheme 3. Possible reaction pathway of deallylation reaction with tBuLi

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

Scheme 5. Reaction pathway of deallylation with SeO2

Scheme 6. Deallylation catalyzed by chromium(Ⅲ)

Scheme 7. Mechanism of the oxidative deallylation with DDQ

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

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

Scheme 10. Mechanism of deallylation with SmI2

Scheme 11. Deallylation promoted by BF3

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

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

Scheme 14. Selective deallylation catalyzed by LVT

Scheme 15. Rh-catalyzed deallylation via isomerization

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

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

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

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

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

Scheme 21. Deallylation of allyl amides catalyzed by Grubbs carbene

Scheme 22. Ruthenium catalyzed deallylation in biological environment

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

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

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

Scheme 26. Mechanism of CoCl2 catalyzed deallylation

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

References 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.

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