苯氧乙酰基四羰基钴催化亚胺与一氧化碳交替共聚反应合成多肽类聚合物

doi:10.7503/cjcu20130435

高等学校化学学报 ›› 2014, Vol. 35 ›› Issue (1): 54.doi: 10.7503/cjcu20130435

苯氧乙酰基四羰基钴催化亚胺与一氧化碳交替共聚反应合成多肽类聚合物

张永坡, 孙怀林()

南开大学化学系, 天津 300071

收稿日期:2013-05-09 出版日期:2014-01-10 发布日期:2013-12-13
作者简介:联系人简介: 孙怀林, 男, 博士, 教授, 博士生导师, 主要从事金属有机化学及催化研究. E-mail:sunhl@nankai.edu.cn
基金资助:
国家自然科学基金(批准号: 20834002)、天津市自然科学基金(批准号: 08JCZDJC21600)和高等学校博士学科点专项科研基金(批准号: 20090031110012)资助

Phenoxyacetylcobalt Tetracarbonyl as Catalyst for Copolymerization of Imines and CO to Produce Polypeptides^†

ZHANG Yongpo, SUN Huailin^*()

Department of Chemistry, Nankai Univeristy, Tianjin 300071, China

Received:2013-05-09 Online:2014-01-10 Published:2013-12-13
Contact: SUN Huailin E-mail:sunhl@nankai.edu.cn
Supported by:
† Supported by the National Natural Science Foundation of China(No.20834002), the Natural Science Foundation of Tianjin, China(No.08JCZDJC21600) and the Research Fund for the Doctoral Program of Higher Education(No.20090031110012)

摘要/Abstract

摘要：

报道了一种新的苯氧乙酰基四羰基钴催化剂, 并将其用于催化亚胺与一氧化碳的交替共聚反应. ¹H NMR分析结果表明, 该催化剂在1个大气压的CO气氛下以烷基钴和酰基钴平衡的形式存在. 催化反应结果表明, 该催化剂具有良好的催化性能, 可以得到具有较高分子量、 N端为苯氧乙酰基的多肽类聚合物, 且具有较窄的分子量分布. 利用核磁共振、红外光谱和质谱等对多肽聚合物的结构进行了表征, 结果表明, 聚合物链终止端除了具有慕尼黑酮类结构的端基以外, 还存在酰胺类的端基, 并对后者的生成机制进行了解释.

关键词: 酰基钴, 烷基钴, 催化剂, 亚胺, 多肽

Abstract:

A new phenoxyacetylcobalt tetracarbonyl catalyst was synthesis and used to catalyze alternating copolymerization of imines and CO. ¹H NMR study indicated that this catalyst existed in the form of an equilebium between the aklycobalt and acylcobalt complexes under 1×10⁵ Pa of CO atmosphere. The results obtained using the catalyst in imines and CO copolymerization demonstrates that this catalyst had good performance, producing polypeptides of high molecular weights, with phenoxyacetyl groups at the starting ends of the polymer chains, and of narrow molecular weight distributions. The structures of polypeptide obtained were characterized by ¹H NMR and ¹³C NMR, IR as well as MALDI-TOF MS methods. It is revealed that at the terminal ends of the polymer chains there exist end groups of amide structures in addition to those observed previously. Possible mechanism for the formation of the amide end groups was provided.

Key words: Acylcobalt, Alkylcobalt, Catalyst, Imine, Polypeptide

中图分类号:

O627.8

TrendMD:

张永坡, 孙怀林. 苯氧乙酰基四羰基钴催化亚胺与一氧化碳交替共聚反应合成多肽类聚合物. 高等学校化学学报, 2014, 35(1): 54.

ZHANG Yongpo, SUN Huailin. Phenoxyacetylcobalt Tetracarbonyl as Catalyst for Copolymerization of Imines and CO to Produce Polypeptides^†. Chem. J. Chinese Universities, 2014, 35(1): 54.

图/表 7

Scheme 1 Synthesis of compound 1

Fig.1 1H NMR spectrum of compound 1 under CO

Scheme 2 Copolymerization of imines and CO catalyzed by compound 1

Table 1 Results of copolymerization of imines and CO catalyzed by compound 1

Entry	Imine	n(M)/n(C)^a	Time/h	Yield(%)	Polypeptide	$M n b$	PDI^c
1	(2)	50∶1	24	100	(4)	8701	1.24
2	(2)	100∶1	36	100	(4)	18032	1.25
3	(3)	50∶1	24	100	(5)	8409	1.17
4	(3)	100∶1	48	100	(5)	18856	1.26

Table 1 Results of copolymerization of imines and CO catalyzed by compound 1

Entry	Imine	n(M)/n(C)^a	Time/h	Yield(%)	Polypeptide	$M n b$	PDI^c
1	(2)	50∶1	24	100	(4)	8701	1.24
2	(2)	100∶1	36	100	(4)	18032	1.25
3	(3)	50∶1	24	100	(5)	8409	1.17
4	(3)	100∶1	48	100	(5)	18856	1.26

Fig.2 1H NMR spectra of polypeptide 4 from Entry 1 in Table 1

Fig.3 MALDI-TOF MS spectra of polypeptide sample 5 obtained from Entry 3 in Table 1 and structures A and B(A) Full spectrum; (B) an expansion of the m/z region from 4430 to 4460; (C) structure of A; (D) structure of B. The m/z difference between peaks of the same type of ions with contiguous n values is 141[e.g. the difference between peaks of (B+K+) with n=29 and n=30, Δm/z=4437.5-4296.4=141.1], which just equals the mass of the repeating unit of the polypeptides.

Scheme 3 Possible mechanism for the formation of amide end groups at the terminal ends of the polypeptide chains

参考文献 22

[1]	Bodanszky M., Bodanszky A., Principles of Peptide Synthesis, 2nd Ed, Springer,New York, 1994, 215—318
[2]	Sewald N., Jakubke H.D., Peptides: Chemistry and Biology, Wiley-VCH,Weinheim, 2002, 61—130
[3]	Zhang D., Lahasky S. H., Guo L., Lee C. U., Lavan M., Macromolecules, 2012, 45, 5833—5841
[4]	Yu L. L., Mao Y. X., Bai X. X., Ran Y., Li A. R., Zhu Y. Y., Yu F., Qu L. B., Chem. J. Chinese Universities, 2013, 34(5), 1166—1173
	(于岚岚, 毛烨炫, 白希希, 冉瑜, 李爱荣, 朱艳艳, 于斐, 屈凌波.高等学校化学学报, 2013,34(5), 1166—1173)
[5]	Deming T. J., Prog. Polym. Sci., 2007, 32, 858—875
[6]	Pattabiraman V. R., Bode J. W., Nature, 2011, 480, 471—479
[7]	Deming T. J., Adv. Mater., 1997, 9, 299—311
[8]	Sen A., Acc. Chem. Res., 1993, 26, 303—310
[9]	Drent E., Budzelaar P. H. M., Chem. Rev., 1996, 96, 663—681
[10]	Kacker S., Kim J. S., Sen A., Angew. Chem. Int. Ed., 1998, 37, 1251—1253
[11]	Dghaym R. D., Yaccato K. J., Arndtsen. B. A., Organometallics, 1998, 17, 4—6
[12]	Cavallo L., J. Am. Chem. Soc., 1999, 121, 4238—4241
[13]	Davis J. L., Arndtsen B. A., Organometallics, 2000, 19, 4657—4659
[14]	Lafrance D., Davis J. L., Dhawan R., Arndtsen B. A., Organometallics, 2001, 20, 1128—1136
[15]	Sun H., Zhang J., Liu Q., Zhao J., Yu L., Angew. Chem. Int. Ed., 2007, 46, 6068—6072
[16]	Edgell W.F., Lyford J., Inorg. Chem., 1970, 9,1932—1933
[17]	Karabatsos G. J., Lande S. S., Tetrahedron, 1967, 24, 3907—3922
[18]	Joly G. D., Jacobsen E. N., J. Am. Chem. Soc., 2004, 126, 4102—4103
[19]	Jia L., Sun H., Shay J. T., Allgeier A. M., Hanton S. D., J. Am. Chem. Soc., 2002, 124, 7282—7283
[20]	Nagy-Gergely I., Szalontai G., Ungváry F., Markó L., Moret M., Sironi A., Zucchi C., Sisak A., Tschoerner C. M., Martinelli A., Sorkau A., Pályi G., Organometallics, 1997, 16, 2740—2742
[21]	Dghaym R. D., Dhawan R., Arndtsen B. A., Angew. Chem. Int. Ed., 2001, 40, 3228—3230
[22]	Speckampa W. N., Hiemstra H., Tetrahedron, 1985, 41, 4367—4416

苯氧乙酰基四羰基钴催化亚胺与一氧化碳交替共聚反应合成多肽类聚合物

Phenoxyacetylcobalt Tetracarbonyl as Catalyst for Copolymerization of Imines and CO to Produce Polypeptides^†

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苯氧乙酰基四羰基钴催化亚胺与一氧化碳交替共聚反应合成多肽类聚合物

Phenoxyacetylcobalt Tetracarbonyl as Catalyst for Copolymerization of Imines and CO to Produce Polypeptides†

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Phenoxyacetylcobalt Tetracarbonyl as Catalyst for Copolymerization of Imines and CO to Produce Polypeptides^†