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

doi:10.6023/cjoc202405031

摘要/Abstract

设计合成了一系列双功能硫脲催化剂用于催化N-羧基环内酸酐(NCA)开环聚合反应生成多肽, 同时固定反应过程中释放的二氧化碳(CO₂), 将其转化成具有工业价值的环状碳酸酯, 通过串联反应实现“一锅法”制备多肽和环状碳酸酯, 提高了原子利用率. 串联反应过程中助引发剂环氧烷烃的加入不但起到活化NCA单体的作用, 还可有效地与CO₂发生环加成反应生成环状碳酸酯. 通过优化催化剂结构和反应条件可极大地提高反应效率, 这一串联方法为原子经济性地合成两种相关化合物提供了新思路.

关键词: 双功能催化剂, 开环聚合, 有机催化, CO₂固定

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

引用此文

王凯悦, 许明诺, 李博, 伍广朋. 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[J]. 有机化学, 2024, 44(10): 3206-3212.

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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参考文献 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.
[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.
[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.)
[22]	Hadjichristidis, N.; Iatrou, H.; Pitsikalis, M.; Sakellariou, G. Chem. Rev. 2009, 109, 5528.
[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