Application of continuous micro-reaction hydrogenation technology in deprotection reaction

doi:10.11949/0438-1157.20201299

Abstract

Abstract:

Protection and deprotection is a common organic synthesis strategy in fine chemical fields such as pharmaceutical intermediates. The commonly used protecting groups are benzyl and benzyloxycarbonyl, which can be removed by catalytic hydrogenation. The conventional high-pressure hydrogenation batch reactors have several drawbacks, such as low mass and heat transfer rate, poor operation safety and slow hydrogenolysis rate. The continuous hydrogenation for heterogeneous catalytic deprotection can achieve high selectivity and significantly shorten the reaction time due to the excellent gas-liquid mass transfer and plug flow characteristics. This paper summarizes the advantages of continuous flow hydrogenation technology in deprotection reaction and its applications in the synthesis of pharmaceutical intermediates, and discusses the effects of catalyst and solvent on the deprotection reaction. Finally, the application of continuous microreaction hydrogenation technology in deprotection is prospected.

Key words: continuous flow, multiphase reaction, deprotection, hydrogenation, microreactor

摘要：

保护与脱保护是医药中间体等精细化工领域中较为常见的一种有机合成策略。常用的保护基主要有苄基与苄氧羰基，通常可利用催化加氢法将其脱除。采用高压加氢间歇釜工艺存在气液传质效率低，操作安全性差，氢解效率低等问题。采用连续微反应加氢技术进行非均相催化加氢脱保护，可以利用其较高的气液传质效率和平推流特性实现高选择性脱保护，并显著缩短反应时间。本文阐述了连续微反应加氢技术在脱保护反应中的优点及其在药物中间体合成中的实际应用，并介绍了催化剂与溶剂对脱保护反应的影响。最后对连续微反应加氢技术在脱保护中的应用进行了展望。

关键词: 连续流, 多相反应, 脱保护, 加氢, 微反应器

CLC Number:

TQ 032.4

LOU Fengyan, YIN Jiabin, DUAN Xiaonan, WANG Qining, AI Ning, ZHANG Jisong. Application of continuous micro-reaction hydrogenation technology in deprotection reaction[J]. CIESC Journal, 2021, 72(2): 761-771.

娄锋炎, 尹佳滨, 段笑南, 王祁宁, 艾宁, 张吉松. 连续微反应加氢技术在脱保护反应中的应用[J]. 化工学报, 2021, 72(2): 761-771.

Figures/Tables 9

References 79

1	Blaser H U, Indolese A, Schnyder A, et al. Supported palladium catalysts for fine chemicals synthesis[J]. Journal of Molecular Catalysis A Chemical, 2001, 173(1): 3-18.
2	Benson H, Bones K, Churchill G, et al. Development of the convergent, kilogram-scale synthesis of an antibacterial clinical candidate using enantioselective hydrogenation[J]. Organic Process Research & Development, 2020, 24(4): 588-598.
3	王灵果, 宋瑛. 活性炭负载Pd(OH)₂催化剂的制备及其在笼形叔胺脱N-苄基上的应用[J]. 河北工业大学学报, 2005, 34(3): 85-88.
	Wang L G, Song Y. Preparation of the active carbon supported palladium catalysts and their application for debenzylation of the caged tertiary amine[J]. Journal of Hebei University of Technology, 2005, 34(3): 85-88.
4	Sowa Jr J. Catalysis of Organic Reactions[M]. California: Taylor & Francis Group, 2005: 510.
5	Gowda D C, Abiraj K. Heterogeneous catalytic transfer hydrogenation in peptide synthesis[J]. Letters in Peptide Science, 2002, 9(4/5): 153-165.
6	Solodenko W, Wen H, Leue S, et al. Development of a continuous-flow system for catalysis with palladium(0) particles[J]. European Journal of Organic Chemistry, 2004, 2004(17): 3601-3610.
7	Daga M C, Taddei M, Varchi G. Rapid microwave-assisted deprotection of N-Cbz and N-Bn derivatives[J]. Tetrahedron Letters, 2001, 42(31): 5191-5194.
8	Mai A H, Borggraeve W M D. Synthesis of N-hydroxypyrazin-2(1H)-ones via selective O-debenzylation of 1-benzyloxypyrazin-2(1H)-ones using flow methodology[J]. Journal of Flow Chemistry, 2015, 5(1): 6-10.
9	Sultane P R, Mete T B, Bhat R G. A convenient protocol for the deprotection of N-benzyloxycarbonyl (Cbz) and benzyl ester groups[J]. Tetrahedron Letters, 2015, 56(16): 2067-2070.
10	Chu L N, Nanduri V B, Patel R N, et al. Enzymes for the removal of N-carbobenzyloxy protecting groups from N-carbobenzyloxy-D- and L-amino acids[J]. Journal of Molecular Catalysis B: Enzymatic, 2013, 85/86: 56-60.
11	周光伟, 张莉珠, 薛亚涵, 等. N-苄基脱除研究进展[J]. 有机化学, 2015, 39(9): 2428-2442.
	Zhou G W, Zhang L Z, Xue Y H, et al. Progress of N-benzyl removal[J]. Chinese Journal of Organic Chemistry, 2015, 66(9): 2428-2442.
12	张强. Caspase-3/7底物的合成及其相关荧光分子合成新方法的研究[D]. 南京: 南京理工大学, 2013.
	Zhang Q. Preparation of the caspase-3/7 substrate and a new systhesis method of fluorescent molecule used in the substrate[D]. Nanjing: Nanjing University of Science & Technology, 2013.
13	Murata M, Hara T, Mori K, et al. Efficient deprotection of N-benzyloxycarbonyl group from amino acids by hydroxyapatite-bound Pd catalyst in the presence of molecular hydrogen[J]. Tetrahedron Letters, 2003, 44(27): 4981-4984.
14	卢定强, 王维胞, 凌岫泉, 等. 新一代喹诺酮类盐酸莫西沙星的合成及应用研究进展[J]. 现代化工, 2014, 34(2): 33-37.
	Lu D Q, Wang W B, Ling X Q, et al. Progress in synthesis and applications of moxifloxacin hydrochloride[J]. Modern Chemical Industry, 2014, 34(2): 33-37.
15	喻理德, 徐其雄, 王星. 莫西沙星侧链合成方法改进[J]. 江西师范大学学报(自然科学版), 2017, 41(5): 507-509.
	Yu L D, Xu Q X, Wang X, et al. The improved synthesis of moxifloxacin side chain[J]. Journal of Jiangxi Normal University(Natural Science Edition), 2017, 41(5): 507-509.
16	陈莉. 催化加氢脱苄基/苄氧羰基的技术研究[D]. 杭州: 浙江工业大学, 2015.
	Chen L. Study on debenzylation/debenzyloxycarbonyl by catalytic hydrogenation methods[D]. Hangzhou: Zhejiang University of Technology, 2015.
17	刘文涛, 郑德强, 王长斌, 等. 多利培南的合成工艺改进[J]. 食品与药品, 2016, 18(6): 404-406.
	Liu W T, Zheng D Q, Wang C B, et al. Improvement on the synthesis process of doripenem[J]. Food and Drug, 2016, 18(6): 404-406.
18	Hwang H T, Martinelli J R, Gounder R, et al. Kinetic study of Pd-catalyzed hydrogenation of N-benzyl-4-fluoroaniline[J]. Chemical Engineering Journal, 2016, 288: 758-769.
19	David A, Vannice M A. Control of catalytic debenzylation and dehalogenation reactions during liquid-phase reduction by H₂[J]. Journal of Catalysis, 2006, 237(2): 349-358.
20	Felpin F X, Fouquet E. A useful, reliable and safer protocol for hydrogenation and the hydrogenolysis of O-benzyl groups: the in situ preparation of an active Pd(0)/C catalyst with well-defined properties[J]. Chemistry-A European Journal, 2010, 16(41): 12440-11245.
21	高金华. 抗菌新药莫西沙星关键中间体的合成研究[D]. 杭州: 浙江工业大学, 2012.
	Gao J H. Study on synthesis of key intermediate of moxifloxacin[D]. Hangzhou: Zhejiang University of Technology, 2012.
22	Kapur M. Synthetic approaches towards polyhydroxy cyclic amines: potent glycosidase inhibitors[D]. Pune: University of Pune, 2002.
23	Yue J. Multiphase flow processing in microreactors combined with heterogeneous catalysis for efficient and sustainable chemical synthesis[J]. Catalysis Today, 2018, 308(15): 3-19.
24	屠佳成, 桑乐, 艾宁, 等. 连续微反应加氢技术在有机合成中的研究进展[J]. 化工学报, 2019, 70(10): 3859-3868.
	Tu J C, Sang L, Ai N, et al. Research process of continuous hydrogenation in organic synthesis[J]. CIESC Journal, 2019, 70(10): 3859-3868.
25	Dormán G, Kocsis L, Jones R, et al. A benchtop continuous flow reactor: a solution to the hazards posed by gas cylinder based hydrogenation[J]. Journal of Chemical Health & Safety, 2013, 20(4): 3-8.
26	Irfan M, Glasnov T N, Kappe C O. Heterogeneous catalytic hydrogenation reactions in continuous‐flow reactors[J]. ChemSusChem, 2011, 4(3): 300-316.
27	Cossar P J, Hizartzidis L, Simone M I, et al. The expanding utility of continuous flow hydrogenation[J]. Organic & Biomolecular Chemistry, 2015, 13(26): 7119-7130.
28	黄建珍. 填充床振荡流反应器中氨曲南主环合成过程[D]. 杭州: 浙江大学, 2014.
	Huang J Z. Synthesis process of 1-azetidinesulfonicacid in a packed-bed oscillatory flow reactor [D]. Hangzhou: Zhejiang University, 2014.
29	Ekholm F S, Mándity I M, Fülöp F, et al. Rapid, simple, and efficient deprotection of benzyl/benzylidene protected carbohydrates by utilization of flow chemistry[J]. Tetrahedron Letters, 2011, 52(16): 1839-1841.
30	Zarandi M, Bayat Y, Zebardasti A, et al. Statistical optimization of a novel approach for the reductive debenzylation of 2,4,6,8,10,12-hexabenzyl-2,4,6,8,10,12-hexaazaisowurtzitane using Pd@SiO₂ nano catalyst[J]. Central European Journal of Energetic Materials, 2017, 14(4): 984-995.
31	Matsunaga Y, Yamada H, Tagawa T. Comparison between upflow reactor and trickle-bed reactor in gas-liquid-liquid-solid four-phase reaction[J]. Journal of Chemical Engineering of Japan, 2009, 42(): 125-129.
32	Fotouhi-Far F, Bashiri H, Hamadanian M, et al. Increment of activity of Pd(OH)₂/C catalyst in order to improve the yield of high performance 2,4,6,8,10,12-hexanitrohexaazaisowurtzitane (HNIW)[J]. Inorganic and Nano-Metal Chemistry, 2017, 47(11): 1489-1494.
33	Tu J C, Sang L, Cheng H, et al. Continuous hydrogenolysis of N-diphenylmethyl groups in a micropacked-bed reactor[J]. Organic Process Research & Development, 2020, 24(1): 59-66.
34	Perosa A, Tundo P, Zinovyev S. Mild catalytic multiphase hydrogenolysis of benzyl ethers[J]. Green Chemistry, 2002, 4(5): 492-494.
35	Oyamada H, Naito T, Kobayashi S. Continuous flow hydrogenation using polysilane-supported palladium/alumina hybrid catalysts[J]. Beilstein Journal of Organic Chemistry, 2011, 7(1): 735-739.
36	Dong K, Chen Y, Zhang Y Y, et al. The highly effective hydrogenolysis-based debenzylation of tetraacetyl-dibenzyl-hexaazaisowurtzitane (TADBIW) using a palladium/DOWEX catalyst having a synergistic effect[J]. Journal of Energetic Materials, 2017, 35(4): 421-429.
37	Lou D, Wang H, Liu S, et al. PdFe bimetallic catalysts for debenzylation of hexabenzylhexaazaisowurtzitane (HBIW) and tetraacetyldibenzylhexaazaisowurtzitane (TADBIW)[J]. Catalysis Communications, 2018, 109: 28-32.
38	Hasegawa K, Sakurai T. Hydrogenolysis catalyst: US20020169074[P]. 2002-11-09.
39	Mead K, Brewer B. Strategies in spiroketal synthesis revisited: Recent applications and advances[J]. Current Organic Chemistry, 2003, 7(3): 227-256.
40	Pandarus V, Béland F, Ciriminna R, et al. Selective debenzylation of benzyl protected groups with SiliaCat Pd(0) under mild conditions[J]. ChemCatChem, 2011, 3(7): 1146-1150.
41	Llàcer E, Romea P, Urpí F. Studies on the hydrogenolysis of benzyl ethers[J]. Tetrahedron Letters, 2006, 47(32): 5815-5818.
42	戴云生, 董守安, 潘再富, 等. 催化氢解脱苄基Pd/C催化剂的研究和应用[J]. 工业催化, 2011, 19(4): 7-10.
	Dai Y S, Dong S A, Pan Z F, et al. Research on and application of Pd/C catalysts for catalytic hydrogenolysis debenzylation[J]. Industrial Catalysis, 2011, 19(4): 7-10.
43	郑纯智, 张继炎, 王日杰. 催化转移加氢及其在有机合成中的应用[J]. 工业催化, 2004, 12(3): 29-35.
	Zheng C Z, Zhang J Y, Wuang R J. Catalytic transfer hydrogenation and its application in organic synthesis [J]. Industrial Catalysis, 2004, 12(3): 29-35.
44	李岳锋, 张之翔, 田勤奋, 等. 美罗培南合成用钯炭催化剂的制备及性能[J]. 工业催化, 2015, 23(6): 464-468.
	Li Y F, Zhang Z X, Tian Q F, et al. Preparation and performance of palladium carbon catalysts for meropenem synthesis[J]. Industrial Catalysis, 2015, 23(6): 464-468.
45	Ji H, Jing Q, Huang J, et al. Acid-facilitated debenzylation of N-Boc, N-benzyl double protected 2-aminopyridinomethyl pyrrolidine derivatives[J]. Tetrahedron, 2012, 68(5): 1359-1366.
46	Bernotas R C, Cube R V. The use of Pearlman's catalyst for selective N-debenzylation in the presence of benzyl Ethers[J]. Synthetic Communications, 1990, 20(8): 1209-1212.
47	Li Y, Manickam G, Ghoshal A, et al. More efficient palladium catalyst for hydrogenolysis of benzyl groups[J]. Synthetic Communications, 2006, 36(7): 925-928.
48	Koskin A P, Simakova I L, Parmon V N. Study of palladium catalyst deactivation in synthesis of 4,10-diformyl-2,6,8,12-tetraacetyl-2,4,6,8,10,12-hexaazaisowurtzitane[J]. Reaction Kinetics and Catalysis Letters, 2007, 92(2): 293-302.
49	Fotouhi‐Far F, Bashiri H, Hamadanian M. Study of deactivation of Pd(OH)₂/C catalyst in reductive debenzylation of hexabenzylhexaazaisowurtzitane[J]. Propellants, Explosives, Pyrotechnics, 2017, 42(2): 213-219.
50	Maksimowski P, Gołofit T, Tomaszewski W. Palladium catalyst in the HBIW hydrodebenzylation reaction. Deactivation and spent catalyst regeneration procedure[J]. Central European Journal of Energetic Materials, 2016, 13(2): 333-348.
51	Fajt V, Kurc L, Červený L. The effect of solvents on the rate of catalytic hydrogenation of 6-ethyl-1,2,3,4-tetrahydroanthracene-9,10-dione[J]. International Journal of Chemical Kinetics, 2008, 40(5): 240-252.
52	Buncel E, Kesmarky S, Symons E A. The inherent instability of dimethylformamide-water systems containing hydroxide ion: further observations[J]. Journal of the Chemical Society D Chemical Communications, 1971, (2): 120.
53	Chen B, Dingerdissen U, Krauter J G E, et al. New developments in hydrogenation catalysis particularly in synthesis of fine and intermediate chemicals[J]. Applied Catalysis A: General, 2005, 280(1): 17-46.
54	Roughley S D, Jordan A M. The medicinal chemist's toolbox: an analysis of reactions used in the pursuit of drug candidates[J]. Journal of Medicinal Chemistry, 2011, 54(10): 3451-3479.
55	Gaunt M J, Yu J, Spencer J B. Rational design of benzyl-type protecting groups allows sequential deprotection of hydroxyl groups by catalytic hydrogenolysis[J]. The Journal of Organic Chemistry, 1998, 63(13): 4172-4173.
56	Sartori G, Ballini R, Bigi F, et al. Protection (and deprotection) of functional groups in organic synthesis by heterogeneous catalysis[J]. Chemical Reviews, 2004, 104(1): 199-250.
57	Sajiki H, Hirota K. A novel type of PdMC‐catalyzed hydrogenation using a catalyst poison: chemoselective inhibition of the hydrogenolysis for O‐benzyl protective group by the addition of a nitrogen‐containing base[J]. Tetrahedron, 1998, 54(46): 13981-13996.
58	Sajiki H, Hirota K. Pd/C-catalyzed chemoselective hydrogenation in the presence of a phenolic MPM protective group using pyridine as a catalyst poison[J]. Chemical & Pharmaceutical Bulletin, 2003, 51(3): 320-324.
59	Yin J, Weisel M, Ji Y, et al. Improved preparation of a key hydroxylamine intermediate for relebactam: rate enhancement of benzyl ether hydrogenolysis with DABCO[J]. Organic Process Research & Development, 2018, 22(3): 273-277.
60	Crawford C, Oscarson S. Optimized conditions for the palladium-catalyzed hydrogenolysis of benzyl and naphthylmethyl ethers: preventing saturation of aromatic protecting groups[J]. European Journal of Organic Chemistry, 2020, 2020(22): 3332-3337.
61	Ochocinska A, Siegbahn A, Ellervik U. HCl/DMF for enhanced chemoselectivity in catalytic hydrogenolysis reactions[J]. Tetrahedron Letters, 2010, 51(39): 5200-5202.
62	Knudsen K R, Holden J, Ley S V, et al. Optimisation of conditions for O-benzyl and N-benzyloxycarbonyl protecting group removal using an automated flow hydrogenator[J]. Advanced Synthesis & Catalysis, 2007, 349(4/5): 535-538.
63	Desai B, Kappe C O. Heterogeneous hydrogenation reactions using a continuous flow high pressure device[J]. Journal of Combinatorial Chemistry, 2005, 7(5): 641-643.
64	Zhang L, Xiao Q, Ma C, et al. Construction of a bicyclic beta-benzyloxy and beta-hydroxy amide library through a multicomponent cyclization reaction[J]. Journal of Combinatorial Chemistry, 2009, 11(4): 640-644.
65	刘巧珍, 江富祥, 王果, 等. Pd/C催化氢化高效脱除含氮糖中的苄基型保护基[J]. 暨南大学学报(自然科学版), 2013, 34(3): 319-323.
	Liu Q Z, Jiang F X, Wang G, et al. High-efficay removal of benzyl-type protective groups in azasugar applying Pd/C catalytic hydrogenation[J]. Journal of Jinan University(Natural Science & Medicine Edition), 2013, 34(3): 319-323.
66	邱文革, 于永忠. N-苄基的脱去[J]. 合成化学, 1998, 6(1): 34-39.
	Qiu W G, Yu Y Z. N-Debenzylation[J]. Chinese Journal of Synthetic Chemistry, 1998, 6(1): 34-39.
67	Bissette A J, Fletcher S P. Comprehensive Organic Synthesis Ⅱ[M]. Oxford: University of Oxford, 2014: 1164-1184.
68	Kovács E, Thurner A, Farkas F, et al. Hydrogenolysis of N-protected aminooxetanes over palladium: an efficient method for a one-step ring opening and debenzylation reaction[J]. Journal of Molecular Catalysis A: Chemical, 2011, 339(1/2): 32-36.
69	Tanielyan S K, Alvez G, Marin N, et al. An unexpected pressure effect in the catalytic hydrogenolysis of a complex benzyl amine[J]. Topics in Catalysis, 2014, 57(17/18/19/20): 1359-1365.
70	Jones R V, Godorhazy L, Varga N, et al. Continuous-flow high pressure hydrogenation reactor for optimization and high-throughput synthesis[J]. Journal of Combinatorial Chemistry, 2006, 8(1): 110-116.
71	Darvas F, Godorhazy L, Karancsi T, et al. Laboratory scale continuous flow hydrogenation process: US7988919[P]. 2011-08-02.
72	Baxendale I R, Hornung C, Ley S V, et al. Flow microwave technology and microreactors in synthesis[J]. Australian Journal of Chemistry, 2013, 66(2): 131-144.
73	Müslehiddinoğlu J, Lobben P, Leung S, et al. A kinetic investigation into the removal of carbobenzyloxy group from protected amines via hydrogenolysis reaction[J]. Catalysis Today, 2007, 123(1/2/3/4): 164-170.
74	Papageorgiou E A, Gaunt M J, Yu J Q, et al. Selective hydrogenolysis of novel benzyl carbamate protecting groups[J]. Organic Letters, 2000, 2(8): 1049-1051.
75	Kobayashi J, Mori Y, Okamoto K, et al. A microfluidic device for conducting gas-liquid-solid hydrogenation reactions[J]. Science, 2004, 304(5675): 1305-1308.
76	Akiyama R, Kobayashi S. The polymer incarcerated method for the preparation of highly active heterogeneous palladium catalysts[J]. Journal of the American Chemical Society, 2003, 125(12): 3412-3413.
77	Kobayashi S, Mori Y, Kitamori T, et al. Method of catalytic reaction using micro-reactor: US7663008[P]. 2010-02-16.
78	Knudsen K R, Ladlow M, Bandpey Z, et al. Fully automated sequence-specific synthesis of α-peptides using flow chemistry[J]. Journal of Flow Chemistry, 2014, 4(1): 18-21.
79	Clapham B, Wilson N S, Michmerhuizen M J, et al. Construction and validation of an automated flow hydrogenation instrument for application in high-throughput organic chemistry[J]. Journal of Combinatorial Chemistry, 2008, 10(1): 88-93.

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