化工产品中氨基的保护与脱保护

doi:10.19286/j.cnki.cci.2022.12.029

Abstract
Figure/Table
References (74)
Related Citation (15)

Download: PDF (0 KB) HTML (1 KB)
Export: BibTeX | EndNote (RIS)

Abstract Based on the activity of amino contained in chemical products, it can participate in a variety of reactions, such as reaction with acid to form salt, acylation of amine (acyl halide, acid anhydride, carboxylic acid, ester can react with ammonia to obtain amide) and aldehyde-ketone reaction, etc., in order to meet the requirements of the target product, it is usually necessary to protect the amino from participating in the reaction. Several common methods of amino protection and deprotection were comprehensively introduced, and the reaction conditions and yield of each method were listed; five kinds of methods, including acylation, alkylation, alkoxy carbonylation, protonation reaction and chelation reaction, and their related examples were summarized, and their advantages and disadvantages were evaluated. The research is helpful to improve the application protection and deprotection of amino in chemical products, and provides a reference for related compounds from exploring synthesis conditions in the laboratory to factory production.

Key words： amine amine protection acylation alkylation alkoxy carbonylation deprotection of amino

	Service

	E-mail this article
	Add to my bookshelf
	Add to citation manager
	E-mail Alert
	RSS
	Articles by authors
	Guo Yanhao
	Hao Qinghui
	Hao Siyuan
	Zhang Yatong
	Su Rong
	Duan Yingmei

Cite this article:

Guo Yanhao,Hao Qinghui,Hao Siyuan等. Protection and deprotection of amino in chemical products[J]. CCI, 2022, 45(12): 106- 112，116..

URL:

http://www.mtyhg.com.cn/EN/10.19286/j.cnki.cci.2022.12.029 OR http://www.mtyhg.com.cn/EN/Y2022/V45/I12/106

[ 1 ] Wuts P G M, Greene W. TW Protective Groups in Organic Synthe- sis[ J ]. 1999. [ 2 ] Ragnarsson U, Grehn L, Maia H L, et al. Enhancing reductive cle- avage of aromatic carboxamides[ J ]. Organic letters, 2001, 3( 13 ): 18 691 - 18 697. [ 3 ] Cavelier F, Enjalbal. Studies of selective Boc removal in the prese- nce of silyl ethers[ J ]. Tetrahedron Letters, 1996, 37( 29 ): 5 131 - 5 134. [ 4 ] Deng J, Hamada Y. Total Synthesis of Alterobactin A, a Super Si- derophore from an Open-Ocean Bacterium [ J ]. J Am Chem Soc, 1995, 117( 29 ): 7 824 - 7 825. [ 5 ] Vuljanic T, Bergquist K E. Piperidine is preferred to morpholine for Fmoc cleavage in solid phase glycopeptide synthesis as exemplified by preparation of glycopeptides related to HIV gp120 and mucins[ J ]. Tetrahedron ,1996, 52( 23 ): 7 983 - 8 000. [ 6 ] Bu X, Xie G, Law C W. An improved deblocking agent for direct Fmoc solid-phase synthesis of peptide thioesters[ J ]. Tetrahedron Lett, 2002, 43( 13 ): 2 419 - 2 422. [ 7 ] Rao T S, Nampalli S, Sekher P. TFA-NHS as bifunctional protect- ing agent: simultaneous protection and activation of amino carboxylic acids[ J ]. Tetrahedron Lett, 2002, 43( 43 ): 7 793 - 7 795. [ 8 ] Mazaleyrat J P, Xie J, Wakselman M. Selective hydrogenolysis of the benzyloxycarbonyl protecting group of N?-lysine in cyclopeptides containing a benzylic phenyl ether function. Evidence for N?-methylated lysine side products[ J ]. Tetrahedron Lett, 1992, 33( 30 ): 4 301 - 4 302. [ 9 ] Hasan A, Stengele K P, Giegrich H. Photolabile protecting groups for nucleosides: Synthesis and photodeprotection rates[ J ]. Tetrahedron 1997, 53( 12 ): 4 247 - 4 264. [ 10 ] Matsubara N, Oiwa K, Hohsaka T. Molecular design of glycoprote- in mimetics: Glycoblotting by engineered proteins with an oxylamino-functionalized amino acid residue[ J ]. I Chem Eur, 2005, 11(23):6 974 - 6 981. [ 11 ] Igarashi J, Kobayashi Y. Improved synthesis of quinine alkaloids with the Teoc protective group[ J ]. Tetrahedron Lett, 2005, 46( 37 ): 6 381-6 384. [ 12 ] Smith A B, Safonov I G, Corbett R M. Total synthesis of (+)-zamp- anolide[ J ]. Am Chem Soc, 2001, 123( 21 ): 12 426 - 12 427. [ 13 ] Barthels R, Kunz H. The 1,3-Dithian-2-ylmethoxycarbonyl (Dm- oc) Moiety-A Protecting Group for the Amino Function in Peptide Synthesis[ J ]. Angew Chem, 1982, 21( 4 ): 292. [ 14 ] Inouye K, Sumitomo Y, Shin M. Synthesis of Corticotropin Peptid- es. XIII. The Synthesis of a Hexacosapeptide and a Heptacosapeptide Corresponding to the First Twenty-six and Twenty-seven Amino Acid Residues of Corticotropin (ACTH)[ J ]. B Chem Sos Jpn, 1976, 49( 12 ): 3 620 - 3 628. [ 15 ] Kunz H. Methylthio athoxycarbonyl-Rest als Zweistufen-Schutz gruppe fur die Aminofunktion in Aminosauren und Peptiden[ J ]. Chem Ber, 1976, 109( 11 ): 3 693 - 3 706. [ 16 ] Kunz H, Barthels R. Der 1,3-Dithian-2-ylmethoxycarbonyl-(Dm oc)-Rest als Zweistufen-Schutzgruppe für die Aminofunktion von Aminosauren und Peptiden[ J ]. Chem Ber, 1982, 115( 3 ): 833 - 845. [ 17 ] Waldmann H, Kunz H. 1,3-Dithian-2-ylmethyl esters as two-st- ep carboxy-protecting groups in the synthesis of N-glycopeptides[ J ]. J Org Chem, 1988, 53( 18 ): 4 172 - 4 175. [ 18 ] 沈宗旋，王亚玲，李新生，等. 胍催化邻苯二甲酰亚胺对环氧化合物的开环反应[ J ]. 化学研究与应用，2003，15（ 3 ）：354 - 356. [ 19 ] Nefkens G H L, Tesser G I, Nivard R J F. A simple preparation of phthaloyl amino acids via a mild phthaloylation[ J ]. Rec Trav Chim, 1960, 79( 7 ): 688 - 698. [ 20 ] Meffre P, Durand P, Le Goffic F. Methyl (S)-2-phthalimido-4-o- xobutanoate[ J ]. Org Syn, 1999, 76: 123. [ 21 ] Aguilar N, Moyano A A. General, Catalytic, and Enantioselective Synthesis of (S)-γ-[(S)-1-Aminoalkyl]-γ-lactones[ J ]. J Org Chem, 1998, 63( 11 ): 3 560 - 3 567. [ 22 ] Wshijun W, Zhujun Y. Total Synthesis of Cyclomarin C[ J ]. Org Lett, 2004, 6( 16 ): 2 721 - 2 724. [ 23 ] Lee, Chang-Hee, Lee, et al. Cis and trans-strapped calix pyrroles bearing phthalamide linkers: Synthesis and anion-binding properties[ J ]. Org Chem, 2005, 70( 6 ): 2 067 - 2 074. [ 24 ] Osby J O, Martin M G, Ganem B. An exceptionally mild deprotec- tion of phthalimides[ J ]. Tetrahedron Lett, 1984, 25( 20 ): 2 093 - 2 096. [ 25 ] 刘国樑. 对甲苯磺酰胺生产新工艺[ J ]. 山西化工, 1990（ 1 ）：27 - 29. [ 26 ] Sakakibara S, Fujii T. Synthesis and use of N-im-tosyl-L-histid- ine[ J ]. Chem Soc Jpn, 1969, 42( 5 ): 1 466. [ 27 ] Arthur G, Schultz , Carlos W, et al. Asymmetric Synthesis of trans -2-Aminocyclohexanecarboxylic Acid Derivatives from Pyrrolobenzodiazepine-5, 11-diones:(1S, 2S)-2-(N-Tosylamino) Cyclohexanecarboxylic Acid[ J ]. Org Syn, 2003, 73: 174. [ 28 ] Masuda Yui, Mori Kenji. Synthesis of (2S,2 ' R,3S,4R)-2-(2 '-hy- droxy-21 '-methyldocosanoylamino)-1,3,4-pentadecanetriol, the ceramide sex pheromone of the female hair crab, Erimacrus isenbeckii[ J ]. Biosci Biotechnol Biochem, 2002, 66( 7 ): 1 531 - 1 537. [ 29 ] Seffar Fatima. Preparation and reactions of 4-, 5-, and 6-methoxy substituted 3-lithioindoles and 3-indolylzinc derivatives[ J ]. Synthesis, 2001, 2 001( 2 ): 267 - 275. [ 30 ] Burgess Kevin, Liu Lee T. Asymmetric syntheses of optically active .alpha.,.beta.-disubstituted .beta.-amino acids.[ J ]. J Org Chem, 1993, 58( 17 ): 4 758 - 4 763. [ 31 ] Kotek Jan, Lebduskova Petra. Lanthanide(III) complexes of novel mixed carboxylic-phosphorus acid derivatives of diethylenetriamine: A step towards more efficient MRI contrast agents[ J ]. Chem Europ, 2003, 9( 23 ): 5 899 - 5 915. [ 32 ] Nenajdenko Valentine G, Karpov Alexei S. A new convenient app- roach to chiral β-aryl(heteroaryl)alkylamines[ J ]. Tetrahedron Asymmetry, 2001, 12( 18 ): 2 517 - 2 527. [ 33 ] Calvisi Giuseppina, Dell-Uomo Natalina. A Practical and Stereoc- onservative Synthesis of (R)-3-Amino-4-(trimethylammonio) butanoate [(R)-Aminocarnitine], and Its Trimethylphosphonium and Simple Ammonium Analogues Starting from d-Aspartic Acid[ J ]. Eur J Org Chem, 2003, 2 003( 23 ): 4 501 - 4 506. [ 34 ] Nenajdenko V G, Karpov A S, Balenkova E S. A new convenient approach to chiral β-aryl (heteroaryl) alkylamines[ J ]. Tetrahedron Asymmetry, 2001, 12( 18 ): 2 517 - 2 527. [ 35 ] Weygand F, Csendes E. N-Trifluoracetyl-aminosauren[ J ]. Ang- ewandte Chemie, 1952, 64( 5 ): 136. [ 36 ] Weygand F, Geiger R. N-Trifluoracetyl-aminosauren, IV. Mitteil.: N-Trifluoracetylierung von Aminosauren in wasserfreier Trifluor- essigsaure[ J ]. Chemische Berichte, 1956, 89( 3 ): 647 - 652. [ 37 ] Chambers James J, Parrish Jeasen C. Synthesis and pharmacologi- cal characterization of a series of geometrically constrained 5-HT2A/2C receptor ligands[ J ]. J Med Chem, 2003, 46( 16 ): 3 526 - 3 535. [ 38 ] Knoops N, Deroover G, Jidong Z, et al. Generation of 3-piperidine (methan) amines and cyclic 3-piperidine-methanamines as potential substance P antagonists[ J ]. Tetrahedron, 1997, 53( 37 ): 12 699 - 12 716. [ 39 ] Whitlock G A, Carreira E M. Enantioselective Synthesis of ent-St- ellettamide A: Asymmetric Dipolar Cycloadditions with Me3SiCHN2[ J ]. Helvetica chimica acta, 2000, 83( 8 ): 2 007 - 2 022. [ 40 ] Chambers J J, Parrish J C, Jensen N H, et al. Synthesis and phar- macological characterization of a series of geometrically constrained 5-HT2A/2C receptor ligands[ J ]. J Med Chem, 2003, 46( 16 ): 3 526 - 3 535. [ 41 ] Hoffman Robert V, Maslouh Najib. Highly Stereoselective Synthe- ses of s yn-and a nti-1, 2-Amino Alcohols[ J ]. J Org Chem, 2002, 67( 4 ): 1 045 - 1 056. [ 42 ] Gros C, Boulègue C, Galeotti N, et al. Stereochemical control in the preparation of α-amino N-methylthiazolidine masked aldehydes used for peptide aldehydes synthesis[ J ]. Tetrahedron, 2002, 58( 13 ): 2 673 - 2 680. [ 43 ] Vago I, Kalaus G, Greiner I. Synthesis of Vinca Alkaloids and Re- lated Compounds 95. Attempted Build-up of the Aspidospermid- ine Skelton by [4+2] Cycloaddition. Some Unexpected Reactions, and Formation of a New Ring System[ J ]. Heterocycles, 2001, 55( 5 ): 873 - 880. [ 44 ] Pickersgill I F, Rapoport H. Preparation of functionalized, confor- mationally constrained DTPA analogues from L-or D-serine and trans-4-hydroxy-L-proline. Hydroxymethyl substituents on the central acetic acid and on the backbone[ J ]. J Org Chem, 2000, 65( 13 ): 4 048 - 4 057. [ 45 ] Ordonez Mario, Cruz-Cordero Ricardo. Highly Diastereoselective Synthesis of anti-γ-N-Benzylamino-β-hydroxyphosphonates[ J ]. Chem Commun, 2004( 6 ): 672 - 673. [ 46 ] Arslautas Enver, Smith-Jones Peter M. TAME-Hex A-A Novel Bifunctional Chelating Agent for Radioimmunoimaging[ J ]. J Org Chem, 2004, 2 004 ( 19 ): 3 979 - 3 984. [ 47 ] Takigawa Y, Ito H, Omodera K, et al. Construction of nitrogen-he- terocyclic compounds through zirconium mediated intramolecular alkene-carbonyl coupling reaction of N-(o-alkenylaryl) carbamate derivatives[ J ]. Tetrahedron, 2004, 60( 6 ): 1 385 - 1 392. [ 48 ] Park S, Kang Y. Reactivities of 2-Aminomethylimidazole: An Ap- proach for a Synthesis of Imidazo [1, 5-a] imidazole[ J ]. Heterocycles, 2002, 57( 12 ): 2 393 - 2 400. [ 49 ] Clayden J, Pink J H, Westlund N, et al. Atroposelectivity in the el- ectrophilic substitution reactions of laterally lithiated and silylated tertiary amides[ J ]. J Am Chem Soc, 2002 ( 7 ): 901 - 917. [ 50 ] Boeckman Jr R K, Nelson S G, Gaul M D. Toward the development of a general chiral auxiliary. Preparation of a new class of camphor lactam imides and their application to the construction of quaternary centers via Diels-Alder cycloaddition[J]. J Am Chem Soc, 1992, 114(6): 2 258-2 260. [51] Gelder Rane De. 6-Spiro-1, 4-diazepane-2, 5-diones by Head-to-Tail N1/C2 Amide Bond Formation[ J ]. Eur J Org Chem, 2005, 5: 907 - 917. [ 52 ] Kawasaki T, Kouko T, Totsuka H, et al. Synthesis of marine bisin- dole alkaloids, hamacanthins A and B through intramolecular transamidation-cyclization[ J ]. Tetrahedron letters, 2003, 44( 49 ): 8 849 - 8 852. [ 53 ] Van Rompaey K, Van den Eynde I, De Kimpe N, et al. A versatile synthesis of 2-substituted 4-amino-1, 2, 4, 5-tetrahydro-2-ben- zazepine-3-ones[ J ]. Tetrahedron, 2003, 59( 24 ): 4 421 - 4 432. [ 54 ] Cossy J, Pévet I, Meyer C. Total Synthesis of (-)-4a, 5-Dihydro- streptazolin[ J ]. Eur J Org Chem, 2001, 2 001( 15 ): 2 841 - 2 850. [ 56 ] Van Rompaey K, Van den Eynde I, De Kimpe N, et al. A versatile synthesis of 2-substituted 4-amino-1, 2, 4, 5-tetrahydro-2-be- nzazepine-3-ones[ J ]. Tetrahedron, 2003, 59( 24 ): 4 421 - 4 432. [ 57 ] Basso A, Banfi L, Riva R, et al. A novel highly selective chiral auxiliary for the asymmetric synthesis of L-and D-α-amino acid derivatives via a multicomponent Ugi reaction[ J ]. J Org Chem, 2005, 70( 2 ): 575 - 579. [ 58 ] Tilekar J N, Patil N T, Jadhav H S, et al. Concise and practical synthesis of (2S, 3R, 4R, 5R) and (2S, 3R, 4R, 5S)-1, 6-dideoxy-1, 6-iminosugars[ J ]. Tetrahedron, 2003, 59( 11 ): 1 873 - 1 876. [ 59 ] Rawal V H, Jones R J, Cava M P. Photocyclization strategy for the synthesis of antitumor agent CC-1065: synthesis of dideoxy PDE-I and PDE-II. Synthesis of thiophene and furan analogs of dideoxy PDE-I and PDE-II[ J ]. J Org Chem, 1987, 52( 1 ): 19 - 28. [ 60 ] Basso A, Banfi L, Riva R, et al. A novel highly selective chiral auxiliary for the asymmetric synthesis of L-and D-α-amino acid derivatives via a multicomponent Ugi reaction[ J ]. J Org Chem, 2005, 70( 2 ): 575 - 579. [ 61 ] Tilekar J N, Patil N T, Jadhav H S, et al. Concise and practical synthesis of (2S, 3R, 4R, 5R) and (2S, 3R, 4R, 5S)-1, 6-dideoxy-1, 6-iminosugars[ J ]. Tetrahedron, 2003, 59( 11 ): 1 873 - 1 876. [ 62 ] Tarbell D S, Yamamoto Y, Pope B M. New method to prepare Nt-butoxycarbonyl derivatives and the corresponding sulfur analogs from di-t-butyl dicarbonate or di-t-butyl dithiol dicarbonates and amino acids[ J ]. Proc Natl Acad Sci, 1972, 69( 3 ): 730 - 732. [ 63 ] Anderson G W, McGregor. Butyloxycarbonyl amino acids and their use in peptide synthesis[ J ]. J Am Chem Sot, 1957, 79: 6 180 - 6 183. [ 64 ] Dondoni A, Perrone D, Turturici E. Synthesis of β-D-galactosyl ceramide methylene isostere[ J ]. J Org Chem, 1999, 64( 15 ): 5 557 -5 564. [ 65 ] Luo Q L, Li J Y, Liu Z Y. Discovery and Structural Modification of Inhibitors of Methionine Aminopeptidases from Escherichia c oli and Saccharomyces c erevisiae[ J ]. J Med Chem, 2003, 46( 13 ): 2 631 - 2 640. [ 66 ] Macleod C, McKiernan G J, Guthrie E J, et al. Synthesis of 2-sub- stituted benzofurans and indoles using functionalized titanium benzylidene reagents on solid phase[ J ]. J Org Chem, 2003, 68( 2 ): 387 - 401. [ 67 ] Hammarstrom L G J, Fu Y, Vail S, et al. A Convenient Preparation of an Orthogonally Protected C α, C α-Disubstituted Amino Acid Analog of Lysine: 1-tert-butyloxycarbonyl-4-((9-fluorenyl- methyloxycarbonyl) amino)-piperidine-4-carboxylic Acid: [1, 4-Piperidinedicarboxylic acid, 4-[[(9 H-fluoren-9-ylmethyloxy) carbonyl] amino]-,(1, 1-dimethylethyl) ester][ J ]. Org Syn, 2003, 81: 213 - 224. [ 68 ] Gan T, Liu R, Yu P, et al. Enantiospecific Synthesis of Optically Active 6-Methoxytryptophan Derivatives and Total Synthesis of Tryprostatin A1[ J ]. J Org Chem, 1997, 62( 26 ): 9 298 - 9 304. [ 69 ] Hynes J, Doubleday W W, Dyckman A J, et al. N-Amination of pyrrole and indole heterocycles with monochloramine (NH2Cl)[ J ]. J Org Chem, 2004, 69( 4 ): 1 368 - 1 371. [ 70 ] Wehbe J, Rolland V, Fruchier A, et al. Enantioselective synthesis of new 4-substituted glutamic acid derivatives[ J ]. Tetrahedron Asymmetry, 2004, 15( 5 ): 851 - 858. [ 71 ] Konda-Yamada Y, Okada C, Yoshida K, et al. Convenient synthe- sis of 7′ and 6′-bromo-D-tryptophan and their derivatives by enzymatic optical resolution using D-aminoacylase[ J ]. Tetrahed- ron, 2002, 58( 39 ): 7 851 - 7 861. [ 72 ] Bravo P, Capelli S, Crucianelli M, et al. Asymmetric synthesis of α-arylglycinols via additions of lithium methyl p-tolyl sulfoxide to N-(PMP) arylaldimines followed by “non oxidative” Pummerer reaction[ J ]. Tetrahedron, 1999, 55( 10 ): 3 025 - 3 040. [ 73 ] Alargov D K, Naydenova Z, Grancharov K, et al. Synthesis of some 5′-O-amino acid derivatives of uridine as potential inhibitors ofUDP-glucuronosyltransferase[ J ]. Monatsh Chem, 1997, 128( 6 ): 725 - 732. [ 74 ] 高旭红，李炳奇. 有机合成中的氨基保护及应用（综述）[ J ]. 石河子大学学报（自然科学版）, 1999（ 1 ）：76 - 86.