环二肽的合成及其不对称诱导效应
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摘要
本文综述了不对称合成的发展,光学活性的环状二肽的合成及其在氰醇化反应中的催化作用和不对称诱导效应。
本文以L-苯丙氨酸、L-组氨酸、L-亮氨酸、L-缬氨酸、L-酪氨酸等为原料,经氨基保护、羧基保护、缩合、加氢脱保护基、环化等步骤合成了六种手性环二肽:环(L-苯丙-L-组)二肽、环(L-苯丙-L-苯丙)二肽、环(L-苯丙-L-缬)二肽、环(L-亮-L-组)二肽、环(L-缬-L-缬)二肽、环(L-缬-L-酪)二肽。通过熔点测定、旋光度测定、IR和HNMR表征了这些环二肽及中间体的结构。合成的环状二肽通过用不同溶剂进行重结晶、得到了聚集状态不同的产品。
应用合成的六种环二肽作为相转移催化剂催化氰醇化反应,验证了它们的催化效果和不对称诱导效应,探索了最佳催化条件,比较了它们的异同。实验结果显示:对于氰醇化反应,合成的六种催化剂都有不同程度的催化作用和不对称诱导效应;相比较而言,cyclo(L-Phe-L-His)的不对称诱导效应较好,光学产率ee%达到40.6%,并依据实验结果和相关原理,讨论了手性环二肽对氰醇化反应的不对称诱导效应机制。
Chiral cyanohydrin is one of the very important intermediates in agrochemical and pharmacy industry. Chiral cyclic dipeptide is an effective catalyst for asymmetric cyanohydrin synthesis. It summarized the development and the recently research work on chiral cyclic dipeptide as catalysis for cyanohydrination process.
We have studied the process of preparation of optically active cyclic dipeptides by condensation of N-terminal protected phenylalanine and C-terminal protected histidine, Pd/C catalytic hydrogenating and cyclizing. Their structures were elucidated by m.p. IR and HNMR. The products were farther treated by fractional crystallized from different solvents .Different processes have given the product different crystal forms.
Experiments were carried out by using dipeptides as catalyst for asymmetric addition of hydrogen cyanide to aldehyde. Servals catalysts were applied to asymmetric addition for being compared. Aldehyde has been coverted to cyanohydrin by using cyclo (L-Phe-L-His) as catalyst in 40.6% enantiomeric excess. A mode for the asymmetric induction of the chiral phase transfer catalyst was suggested on the basis of the results of the experiment and the relate theory.
本文以L-苯丙氨酸、L-组氨酸、L-亮氨酸、L-缬氨酸、L-酪氨酸等为原料,经氨基保护、羧基保护、缩合、加氢脱保护基、环化等步骤合成了六种手性环二肽:环(L-苯丙-L-组)二肽、环(L-苯丙-L-苯丙)二肽、环(L-苯丙-L-缬)二肽、环(L-亮-L-组)二肽、环(L-缬-L-缬)二肽、环(L-缬-L-酪)二肽。通过熔点测定、旋光度测定、IR和HNMR表征了这些环二肽及中间体的结构。合成的环状二肽通过用不同溶剂进行重结晶、得到了聚集状态不同的产品。
应用合成的六种环二肽作为相转移催化剂催化氰醇化反应,验证了它们的催化效果和不对称诱导效应,探索了最佳催化条件,比较了它们的异同。实验结果显示:对于氰醇化反应,合成的六种催化剂都有不同程度的催化作用和不对称诱导效应;相比较而言,cyclo(L-Phe-L-His)的不对称诱导效应较好,光学产率ee%达到40.6%,并依据实验结果和相关原理,讨论了手性环二肽对氰醇化反应的不对称诱导效应机制。
Chiral cyanohydrin is one of the very important intermediates in agrochemical and pharmacy industry. Chiral cyclic dipeptide is an effective catalyst for asymmetric cyanohydrin synthesis. It summarized the development and the recently research work on chiral cyclic dipeptide as catalysis for cyanohydrination process.
We have studied the process of preparation of optically active cyclic dipeptides by condensation of N-terminal protected phenylalanine and C-terminal protected histidine, Pd/C catalytic hydrogenating and cyclizing. Their structures were elucidated by m.p. IR and HNMR. The products were farther treated by fractional crystallized from different solvents .Different processes have given the product different crystal forms.
Experiments were carried out by using dipeptides as catalyst for asymmetric addition of hydrogen cyanide to aldehyde. Servals catalysts were applied to asymmetric addition for being compared. Aldehyde has been coverted to cyanohydrin by using cyclo (L-Phe-L-His) as catalyst in 40.6% enantiomeric excess. A mode for the asymmetric induction of the chiral phase transfer catalyst was suggested on the basis of the results of the experiment and the relate theory.
引文
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[4] Vello R.A.,Koomen G.J.,Tetrahedron:Asymm.,1993,4,2401
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[8] A)Izumi T, Fukaya K. Bull. Baker's yeast reduction of α- (acylamino)acetopheno nes and lipase catalyzed resolution of -α-acylamino-1-aryletanols.Chem Soc Jpn , 1993, 66:1216. B)Vanttinen E, Kanerva L T.Combination of the lipase-catalyzed resolution with the Mitsunbu esterfication in one-pot. Tetrahedron Asym. 1995, 6:1779-1786.
[9] Menendez E,Brieva R. Optically-active (S)-ketone-cyanohydrin and aldehyde-cy anohydrin via an (R)-oxynitrilase catalyzed transcyanation Chemoenzymatic syntheses of 2-cyanotetrahydrofuran and 2-cyanotetrahydropyran. J Chem Soc Chem Commun, 1995, 95:989.
[10] Mistada S, Yamamoto H, Umemura T, Hirohara H, Nabeshima S. ArgiBoil Chem, 1990,54(11): 2907.
[11] Kanerva L T. Acta. J. Chem. Scand, 1996, 50:234.
[12] 叶秀林 .立体化学 , 北京大学出版社, 289-290
[13] 周维善,庄治平著.不对称合成[M].北京:科学出版社,1997.1-91.
[14] Knowles,W、S.,SabackyM .J.J.Chem.Soc, Chem.Commu.,1968,1445;
[15] 蒋耀忠,周向葛,胡文浩.手性催化剂与不对称反应[J].化学研究与应用,1993, 5(3):1-11.
[16] Katsuki T,Sharpless K B.The first practical method for asymmetric epoxidation[J].Am Chem Soc,1980,102(18):5974-5976
[17] Klunder J M,Onami T,Sharpless K B.Arenesulfonate derivatives of homochiral glycido1:versatile chiral building blocks for organic synthesis[J].J Org Chem,1989,54(6):1295-1304.
[18] Jacobsen E N,Istvan M,William S,et a1.Asymmetric dihydroxylation via ligand-accelerated catalysis[J]. J Am Chem Soc,1988,110(6):1968-1970.
[19] Wang Z.M,Hartmuth C K,SharpLess K B.Large-scale and highly enantioselective synthesis of the taxol C-13 side chain through asymmetric dihydroxylation[J].J. Org. Chem,1994,59(17):5104-5105.
[20] 林国强著.手性合成---不对称反应及其应用[M]. 北京:科学出版,2000.1-34.
[21] Corey E J,Xu.F,Noe M C.A rational approach to catalytic enantioselective enolate alkylation using a structurally rigidified and defined chiral quaternary ammonium salt under phase-transfer catalysis[J].J Am Chem Soc,1997,119:12 414-12 415.
[22] Walborsky.H.M.Barash.L.,Davis.T.C.,J.Org.Chem. 1961.26.4478;
[23] 谢斌,冯建申,邹立科等.金属有机化合物在催化不对称合成中的应用[J]. 四川理工学院学报(自然科学版)2006 19(2):90～96
[24] Morrison J.D, Mosher H S. Asymmetric organic reactions[J].Prentice-Hall, Englewood-Cliff, N.J., 1971:13.
[26] 张滂主编.有机合成进展[M].北京:科学出版社,1992, 105.
[27].(a) Smtskamp-Wilms, E.; Brussee, J.; and van det Gen A.; Recl. Trav. Chim.Pay s-B as 1991,110,209 (b)Efenberger,F. ; Angew.Chem.Int.Ed.Engl.1994,33, 1555 .(c )E fenberger,F. ; Enantiomer.1996,1,359.(d )Griengl,H .;Hickel,A .;Joh n,D.V; Kratky,C .;Schmidt, M .;Schwab,H .;J Chem.Soc.,Chem.C ommum.1997, 1933.
[28] (a)Kim,H;J Jackson, W.,R.;Tetrahedron:Asymmetry 1994,5(8):1541. (b)Brown,R.F,C.; Jackson,W,R. ;Maccartby,T,.D;Tetrahedron Asymmetry 1993,4(2),205.
[29] Tararo V.I..Hibbs,D.,E.;Hursthouser,T.,B.; J Chem.Soc, Chem.Commum1998,387.
[30] Reetz M T, Kyung S H et al. Chem. Ind. 1986, (23):818
[31] Narasaka K, YamadaT et al. Chem. Lett., 1987, (10):2073-2075
[32] a) Hayashi M,MatsudaT et al. J. Chem. Soc., Chem. Commun.1990, (19):1364- 1365 b) Hayashi M, Matsuda T et al. J. Chem. Soc., Perkin Trans.I. 1992, (22):3135- 3142
[33] Callant D, Stanssens D et al. Tetrahedron: Asymmetry. 1993, 4(2):185-188
[34] Belokon Y, Ikonnikov N et al. Tetrahedron: Asymmetry. 1996, 7(3):851-855
[35] Jiang Y.Z., Zhou X.G. et al. Tetrahedron: Asymmetry. 1995, 6(2):405-40
[36] a)Hayashi M, Miyamoto Y et al.J.Chem.Soc., Chem. Commun. 1991, (24): 1752- 1753 b)Hayashi M, Inoue T et al. Tetrahedron, 1994, 50 (15):4385- 4395
[37] 钟军. 手性金属试剂催化的不对称羟氰化反应[J] 化学通报. 1998 (5): 43-47
[38] 孙伟,夏春谷. 手性金属 Salen 配合物在不对称催化中的应用[J] 化学进展 2002,14(1): 8-17
[39] 冯小明, 龚流柱. 手性 Schiff Base-Ti(OR)4 配合物催化醛的不对称硅腈化反应[J]高等学校化学学报. 1998, 19(9).1416-1421
[40] Corey E J, Wang Z. Tetrahedron Lett. 1993, 34(25):4001-4004
[41] Kobayashi S, Tsuchiya Y et al. Chem. Lett. 1991, (4):541-544
[42] Abiko A, Wang G Q. Org. Chem. [J]. 1996, 61(7): 2264-2276
[43] Dalton, Dennis M., Garner, Charles M., Fernandez, Jesus M., Gladysz, J. A. (Dep.Chem., Univ. Utah, Salt Lake City, UT 84112, USA) [J] J.Org. Chem. 1991.
[44] Stoutonie D W,Tiemen C H,Dong W.Optica]ly active cyanomethyl esters[P] EP109 681 1984.
[45] JacksonW,R,JuyatilakeG S,Mathrew B R,Wishere C.Exckuation of some cyclic dipeptides as catalyst for the asymmetrichydrocyanation of aldehydes[J] Aust J Chem,1988,41(2):203:
[46] Mori A,Nitta H,Kudo M S,Inoue S Peptide-metal complex as an asymmetric catalyst-A catalysticenantioselective cyanhydrins synthesis [J] Tetrahedron Lett,1991,32(34): 4333～4336
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