Application of Bifunctional Thiourea Catalyst in One Pot Preparation of Polypeptides and Cyclic Carbonates

doi:10.6023/cjoc202405031

Chinese Journal of Organic Chemistry ›› 2024, Vol. 44 ›› Issue (10): 3206-3212.DOI: 10.6023/cjoc202405031 Previous Articles Next Articles

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双功能硫脲催化剂在“一锅法”制备多肽和环状碳酸酯反应中的应用

王凯悦^a, 许明诺^a, 李博^a^,^*(), 伍广朋^b^,^*()

a 杭州师范大学材料化学与化工学院杭州 310036
b 浙江大学高分子科学与工程学系杭州 310058

收稿日期:2024-05-24 修回日期:2024-08-06 发布日期:2024-08-30
基金资助:
杭州师范大学开放课题基金(KFJJ2023005)

Application of Bifunctional Thiourea Catalyst in One Pot Preparation of Polypeptides and Cyclic Carbonates

Kaiyue Wang^a, Mingnuo Xu^a, Bo Li^a,*(), Guangpeng Wu^b,*()

a College of Material, Chemistry and Chemical Engineering, Hangzhou Normal University, Hangzhou 310036
b Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 310058

Received:2024-05-24 Revised:2024-08-06 Published:2024-08-30
Contact: *E-mail: boli@hznu.edu.cn;gpwu@zju.edu.cn
Supported by:
Hangzhou Normal University(KFJJ2023005)

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Abstract

A series of bifunctional thiourea catalysts were designed and synthesized to catalyze the ring-opening polymerization (ROP) of α-amino acid N-carboxyanhydrides (NCA) for preparation of polypeptides. At the same time, the released carbon dioxide (CO₂) during the reaction was fixed and converted into cyclic carbonates with industrial value. One-pot synthesis of well-defined polyesters and cyclic carbonates in high yields was successfully realized by this tandem process, which increased the atomic utilization. We disclosed that this tandem reaction was processed in the presence of propylene oxide (PO), which was not only judiciously added as an in situ activator for the efficient ROP of NCA, but also reacted with CO₂ in the next step to form cyclic carbonates. By exploring the effect of different structures of bifunctional thiourea catalysts and reaction conditions on the reaction activity, the reaction efficiency could be highly improved. This tandem process offered unprecedented opportunities for the atom-efficient production of two relevant compounds.

Key words: bifunctional catalyst, ring-opening polymerization, organic catalysis, CO₂ fixation

Cite this article

Kaiyue Wang, Mingnuo Xu, Bo Li, Guangpeng Wu. Application of Bifunctional Thiourea Catalyst in One Pot Preparation of Polypeptides and Cyclic Carbonates[J]. Chinese Journal of Organic Chemistry, 2024, 44(10): 3206-3212.

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Fig. & Tab. 4

References 35

[1]	Deming, T. J. Prog. Polym. Sci. 2007, 32, 858.
[2]	Deng, C.; Wu, J.; Cheng, R.; Meng, F.; Klok, H.; Zhong, Z. Prog. Polym. Sci. 2014, 39, 330.
[3]	Lu, H.; Wang, J.; Song, Z.; Yin, L.; Zhang, Y.; Tang, H.; Tu, C.; Lin, Y.; Cheng, J. Chem. Commun. 2014, 50, 139.
[4]	Deming, T. J. Adv. Drug Delivery Rev. 2002, 54, 1145.
[5]	Kataoka, K.; Harada, A.; Nagasaki, Y. Adv. Drug Delivery Rev. 2012, 64, 37.
[6]	Dos Santos, S.; Chandravarkar, A.; Mandal, B.; Mimna, R.; Murat, K.; Saucède, L.; Tella, P.; Tuchscherer, G.; Mutter, M. J. Am. Chem. Soc. 2005, 127, 11888.
[7]	Sang, P.; Shi, Y.; Huang, B.; Xue, S.; Odom, T.; Cai, J. Acc. Chem. Res. 2020, 53, 2425.
[8]	Song, Z.; Fu, H.; Wang, R.; Pacheco, L. A.; Wang, X.; Lin, Y. Chem. Soc. Rev. 2018, 47, 7401.
[9]	Tan, J.; Tay, J.; Hedrick, J.; Yang, Y. Y. Biomaterials 2020, 252, No. 120078.
[10]	Lv, S.; Wu, Y.; Cai, K.; He, H.; Li, Y.; Lan, M.; Chen, X.; Cheng, J.; Yin, L. J. Am. Chem. Soc. 2018, 140, 1235.
[11]	Mowery, B. P.; Lee, S. E.; Kissounko, D. A.; Epand, R. F.; Epand, R. M.; Weisblum, B.; Stahl, S. S.; Gellman, S. H. J. Am. Chem. Soc. 2007, 129, 15474.
[12]	Song, Z.; Tan, Z.; Cheng, J. Macromolecules 2019, 52, 8521.
[13]	Li, P.; Dong, C. M. ACS Macro Lett. 2017, 6, 292.
[14]	Tian. Z. Y.; Zhang. Z.; Wang. S.; Lu. H. Nat. Commun. 2021, 12, 5810
[15]	Chen, C.; Fu, H.; Baumgartner, R.; Song, Z. Y.; Lin, Y; Cheng, J. J. J. Am. Chem. Soc. 2019, 141, 8680.
[16]	Zhao, W.; Lv, Y.; Li, J.; Feng, Z. H.; Ni, Y. H.; Hadjichristidis, N. Nat. Commun. 2019, 10, 3590. doi: 10.1038/s41467-019-11524-y pmid: 31399569
[17]	Wu, Y.; Chen, K.; Wu, X.; Liu, L.; Zhang, W.; Ding, Y.; Liu, S.; Zhou, M.; Shao, N.; Ji, Z.; Chen, J.; Zhu, M.; Liu, R. S. Angew. Chem., Int. Ed. 2021, 60, 26063.
[18]	Rasines Mazo, A.; Allison-Logan, S.; Karimi, F.; Chan, N. J.; Qiu, W.; Duan, W.; O’Brien-Simpson, N. M.; Qiao, G. G. Chem. Soc. Rev. 2020, 49, 4737. doi: 10.1039/c9cs00738e pmid: 32573586
[19]	Hu, S.; Zhao, J.; Zhang, G.; Schlaad, H. Prog. Polym. Sci. 2017, 74, 34.
[20]	Yan, J.; Liu, K.; Li, W.; Shi, H.; Zhang, A. Macromolecules 2016, 49, 510.
[21]	Zhang, Z. C.; Xiong, W.; Lu, H. Acta Chim. Sinica 2023, 81, 1113. (in Chinese)
	(张正初, 熊炜, 吕华, 化学学报, 2023, 81, 1113.) doi: 10.6023/A23050211
[22]	Hadjichristidis, N.; Iatrou, H.; Pitsikalis, M.; Sakellariou, G. Chem. Rev. 2009, 109, 5528. doi: 10.1021/cr900049t pmid: 19691359
[23]	Deming, T. J. J. Am. Chem. Soc. 1997, 119, 2759.
[24]	Peng, Y. L.; Lai, S. L.; Lin, C. C. Macromolecules 2008, 41, 3455.
[25]	Peng, H.; Chen, W. L.; Kong, J.; Shen, Z. Q.; Ling, J. Chin. J. Polym. Sci. 2014, 32, 743.
[26]	Zhang, H. Y.; Nie, Y. Z.; Zhi, X. M.; Du, H. F.; Yang, J. Chem. Commun. 2017, 53, 5155.
[27]	Yuan, J. S.; Zhang, Y.; Li, Z. Z.; Wang, Y. Y.; Lu, H. ACS Macro Lett. 2018, 7, 892.
[28]	Wu, Y.; Zhang, D.; Ma, P.; Zhou, R.; Hua, L.; Liu, R. Nat. Commun. 2018, 9, No. 5297.
[29]	Lu, H.; Cheng, J. J. Am. Chem. Soc. 2007, 129, 1411.
[30]	Lv, W.; Wang, Y.; Li, M.; Wang, X.; Tao, Y. J. Am. Chem. Soc. 2022, 144, 23622.
[31]	Wang, K. Y.; Li, Z. Q.; Xu, M. N.; Li, B. Macromolecules 2023, 56, 5599.
[32]	Li, Z. Q.; Zhang, Y. Y.; Zheng, Y. J.; Li, B.; Wu, G. P. J. Org. Chem. 2022, 87, 3145.
[33]	Raman, S. K.; Brulé, E.; Tschan, M. J. L.; Thomas, C. M. Chem. Commun. 2014, 50, 13773.
[34]	Jia, F.; Chen, X.; Zheng, Y.; Qin, Y. S.; Tao, Y. H.; Wang, X. H. Chem. Commun. 2015, 51, 8504.
[35]	Tang, J.; Li, M.; Wang, X.; Tao, Y. H. Angew. Chem., Int. Ed. 2022, 61, e202115465.

Entry^a	Cat.	M/I^b	t/h	T/℃	Yield^c/%	M_n (M_n*)^d/kDa	M_w/M_n^d
1	[BnMe₂NBu][Br]	100/1	2	100	100/35	7.1 (7.9)	1.54
2	[BnMe₂NBu][Br]/TU (1/1)	100/1	2	100	100/48	9.5 (10.8)	1.46
3	[BnMe₂N-C₃-TUPh][Br]	100/1	2	100	100/56	11.2 (12.7)	1.30
4	[BnMe₂N-C₄-TUPh][Br]	100/1	2	100	100/58	13.8 (13.1)	1.28
5	[BnMe₂N-C₅-TUPh][Br]	100/1	2	100	100/59	14.5 (13.6)	1.26
6	[BnMe₂N-C₅-TUPh][Br]	100/1	4	100	100/78	15.8 (17.5)	1.28
7	[BnMe₂N-C₅-TUPh][Br]	100/1	12	100	100/95	20.4 (21.2)	1.30
8	[BnMe₂N-C₅-TUPh][Cl]	100/1	2	100	100/38	7.5 (8.7)	1.32
9	[BnMe₂N-C₅-TUPh][I]	100/1	2	100	100/68	13.9 (15.4)	1.33
10	[BnMe₂N-C₅-TUPh][Br]	50/1	2	100	100/72	6.8 (8.3)	1.24
11^e	[BnMe₂N-C₅-TUPh][Br]	50/1	2	100	100/85	8.6 (9.7)	1.27
12	[BnMe₂N-C₅-TUPh][Br]	100/1	2	25	100/5	2.0 (1.5)	1.18
13	[BnMe₂N-C₅-TUPh][Br]	100/1	2	40	100/16	4.5 (3.9)	1.16
14	[BnMe₂N-C₅-TUPh][Br]	100/1	2	60	100/42	8.2 (9.6)	1.21
15	[BnMe₂N-C₅-TUPh][Br]	100/1	2	120	100/54	11.4 (12.3)	1.33

Entry^a	Cat.	M/I^b	t/h	T/℃	Yield^c/%	M_n (M_n*)^d/kDa	M_w/M_n^d
1	[BnMe₂NBu][Br]	100/1	2	100	100/35	7.1 (7.9)	1.54
2	[BnMe₂NBu][Br]/TU (1/1)	100/1	2	100	100/48	9.5 (10.8)	1.46
3	[BnMe₂N-C₃-TUPh][Br]	100/1	2	100	100/56	11.2 (12.7)	1.30
4	[BnMe₂N-C₄-TUPh][Br]	100/1	2	100	100/58	13.8 (13.1)	1.28
5	[BnMe₂N-C₅-TUPh][Br]	100/1	2	100	100/59	14.5 (13.6)	1.26
6	[BnMe₂N-C₅-TUPh][Br]	100/1	4	100	100/78	15.8 (17.5)	1.28
7	[BnMe₂N-C₅-TUPh][Br]	100/1	12	100	100/95	20.4 (21.2)	1.30
8	[BnMe₂N-C₅-TUPh][Cl]	100/1	2	100	100/38	7.5 (8.7)	1.32
9	[BnMe₂N-C₅-TUPh][I]	100/1	2	100	100/68	13.9 (15.4)	1.33
10	[BnMe₂N-C₅-TUPh][Br]	50/1	2	100	100/72	6.8 (8.3)	1.24
11^e	[BnMe₂N-C₅-TUPh][Br]	50/1	2	100	100/85	8.6 (9.7)	1.27
12	[BnMe₂N-C₅-TUPh][Br]	100/1	2	25	100/5	2.0 (1.5)	1.18
13	[BnMe₂N-C₅-TUPh][Br]	100/1	2	40	100/16	4.5 (3.9)	1.16
14	[BnMe₂N-C₅-TUPh][Br]	100/1	2	60	100/42	8.2 (9.6)	1.21
15	[BnMe₂N-C₅-TUPh][Br]	100/1	2	120	100/54	11.4 (12.3)	1.33

双功能硫脲催化剂在“一锅法”制备多肽和环状碳酸酯反应中的应用

Application of Bifunctional Thiourea Catalyst in One Pot Preparation of Polypeptides and Cyclic Carbonates

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[6]	TENG Ya-Di, SUN Chi-Yu, SHENG Yong-Gang, WANG Shu-Li. Progress in Synthesis and Application of Cyclosilazanes (1)— Cyclodisilazanes [J]. Chin. J. Org. Chem., 2011, 31(06): 932-945.
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