t-BuOLi Catalyzed Esterification of N-Benzyl-N-Boc-amides with Carbohydrates

doi:10.6023/cjoc202401037

Chinese Journal of Organic Chemistry ›› 2024, Vol. 44 ›› Issue (9): 2924-2932.DOI: 10.6023/cjoc202401037 Previous Articles Next Articles

ARTICLES

叔丁醇锂催化N-苄基-N-叔丁氧羰基酰胺与糖的酯化反应

叶丹锋^a^,^*(), 徐冰^a, 万云辉^b^,^*()

a 宁波工程学院材料与化学工程学院浙江宁波 315211
b 上海中医药大学中药学院上海 201203

收稿日期:2024-01-30 修回日期:2024-04-07 发布日期:2024-04-30
通讯作者: 叶丹锋, 万云辉
基金资助:
宁波工程学院启动基金(2130011540027)

t-BuOLi Catalyzed Esterification of N-Benzyl-N-Boc-amides with Carbohydrates

Danfeng Ye^a(), Bing Xu^a, Yunhui Wan^b()

a College of Material Science and Chemical Engineering, Ningbo University of Technology, Ningbo, Zhejiang 315211
b School of Pharmacy, Shanghai University of Traditional Chinese Medicine, Shanghai 201203

Received:2024-01-30 Revised:2024-04-07 Published:2024-04-30
Contact: Danfeng Ye, Yunhui Wan
Supported by:
Startup Foundation of Ningbo University of Technology(2130011540027)

1. .pdf(1196KB)

Abstract

Based on a strategy of ground-state destabilisation of the N—C bond, a general protocol for the esterification of amides with carbohydrates was reported. This protocol offers mild reaction conditions, excellent yields, and broad substrate compatibility, thereby demonstrating great potential for the synthesis of glycoconjugates. Additionally, this method provides an alternative approach for addressing the challenging task of esterifying sterically hindered secondary hydroxyl group of carbohydrates and paving the way for advancements in carbohydrate-based pharmaceuticals.

Key words: t-BuOLi, N-benzyl-N-Boc-amides, esterification, glycoconjugates

Cite this article

Danfeng Ye, Bing Xu, Yunhui Wan. t-BuOLi Catalyzed Esterification of N-Benzyl-N-Boc-amides with Carbohydrates[J]. Chinese Journal of Organic Chemistry, 2024, 44(9): 2924-2932.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 6

Scheme 1. (a) Representative glycoconjugates with biological activity; (b) strategy of ground-state destabilization of amides; (c) previous work: Cs2CO3 catalyzed esterification of activated amides with alkyl alcohol; (d) This work: t-BuOLi catalyzed esterification of activated amides with carbohydrate

Entry	Deviation from the standard condition	Yield^b/%
1	None	88
2	Cs₂CO₃ instead of t-BuOLi	23
3	K₂CO₃ instead of t-BuOLi	nd^c
4	KF instead of t-BuOLi	nd
5	t-BuOK instead of t-BuOLi	nd
6	DIPEA instead of t-BuOLi	nd
7	No base	nd
8	DMA instead of DMF	81
9	DMSO instead of DMF	56
10	CH₃CN instead of DMF	15
11	THF instead of DMF	nd
12	1,4-dioxane instead of DMF	8

Table 1. Optimization for the esterification of amidea

Scheme 2. Scope of N-Boc-N-benzyl amides (isolated yields)

Scheme 3. Esterification of amides with carbohydrates bearing primary hydroxyl group a 2.0 equiv. of t-BuOLi was added and other conditions remain the same.

Scheme 4. Successive esterification of carbohydrate having both primary and secondary hydroxyl groups (isolated yields)

Scheme 5. Probable mechanism for the esterification of N-Boc- N-benzyl amides

References 16

[1]	(a) Huang, M.; Li, J.-J.; Zhang, C. Green Chem. 2023, 25, 9187.
	(b) Liu, J.; Parker, M. F. L.; Wang, S.; Flavell, R. R.; Toste, F. D.; Wilson, D. M. Chem 2021, 7, 2245.
	(c) Meng, G.; Zhang, J.; Szostak, M. Chem. Rev. 2021, 121, 12746.
	(d) Zeng, L.; Xu, S.; Cui, S.; Zhang, F. Org. Chem. Front. 2022, 9, 3757.
[2]	(a) Glatzhofer, D. T.; Roy, R. R.; Cossey, K. N. Org. Lett. 2002, 4, 2349. pmid: 12098244
	(b) Toyao, T.; Nurnobi Rashed, M.; Morita, Y.; Kamachi, T.; Hakim Siddiki, S. M. A.; Ali, M. A.; Touchy, A. S.; Kon, K.; Maeno, Z.; Yoshizawa, K.; Shimizu, K.-I. ChemCatChem 2019, 11, 449. pmid: 12098244
[3]	(a) Hie, L.; Fine Nathel, N. F.; Shah, T. K.; Baker, E. L.; Hong, X.; Yang, Y.-F.; Liu, P.; Houk, K. N.; Garg, N. K. Nature 2015, 524, 79.
	(b) Hie, L.; Baker, E. L.; Anthony, S. M.; Desrosiers, J.-N.; Senanayake, C.; Garg, N. K. Angew. Chem., Int. Ed. 2016, 55, 15129.
[4]	Bourne-Branchu, Y.; Gosmini, C.; Danoun, G. Chem.-Eur. J. 2017, 23, 10043. doi: 10.1002/chem.201702608 pmid: 28594064
[5]	Rahman, M. M.; Li, G.; Szostak, M. J. Org. Chem. 2019, 84, 12091.
[6]	Wu, H.; Guo, W.; Daniel, S.; Li, Y.; Liu, C.; Zeng, Z. Chem.-Eur. J. 2018, 24, 3444.
[7]	(a) Huang, C.; Li, J.; Wang, J.; Zheng, Q.; Li, Z.; Tu, T. Sci. China: Chem. 2021, 64, 66.
	(b) Ding, H.; Qi, W.-Y.; Zhen, J.-S.; Ding, Q.; Luo, Y. Tetrahedron Lett. 2020, 61, 152444.
[8]	(a) La Ferla, B.; Airoldi, C.; Zona, C.; Orsato, A.; Cardona, F.; Merlo, S.; Sironi, E.; D'Orazio, G.; Nicotra, F. Nat. Prod. Rep. 2011, 28, 630.
	(b) Davis, A. P. Chem. Soc. Rev. 2020, 49, 2531.
[9]	(a) Xu, J.; Du, H.; Shi, H.; Song, J.; Yu, J.; Zhou, Y. J. Exp. Bot. 2023, 74, 6119. pmid: 36703321
	(b) Bissette, A. J. Commun. Chem. 2020, 3, 115. doi: 10.1038/s42004-020-00352-7 pmid: 36703321
[10]	(a) Lv, Z.; Liu, H.; Hao, H.; Rahman, F.-U.; Zhang, Y. Eur. J. Med. Chem. 2023, 249, 115164.
	(b) Liet, B.; Laigre, E.; Goyard, D.; Todaro, B.; Tiertant, C.; Boturyn, D.; Berthet, N.; Renaudet, O. Chem. Eur. J. 2019, 25, 15429.
	(c) Shi, B.; Chen, Y.; Geng, M. ; Zhu, D.; Yu, B. Chin. J. Chem. 2023, 41, 891.
[11]	(a) Apicella, M. Front. Cell. Infect. Microbiol. 2012, 2, 1.
	(b) Zhao, M.; Zhu, Y.; Wang, H.; Zhang, W.; Mu, W. Synth. Syst. Biotechnol. 2023, 8, 509.
[12]	Kubo, S.; Mimaki, Y.; Terao, M.; Sashida, Y.; Nikaido, T.; Ohmoto, T. Phytochemistry 1992, 31, 3969.
[13]	(a) Morzycki, J. W.; Wojtkielewicz, A. Phytochem. Rev. 2005, 4, 259.
	(b) Tang, Y.; Li, N.; Duan, J.-A.; Tao, W. Chem. Rev. 2013, 113, 5480.
[14]	(a) Walther, R.; Zelikin, A. N. Adv. Drug Delivery Rev. 2021, 171, 62.
	(b) Zhang, P.; Woen, S.; Wang, T.; Liau, B.; Zhao, S.; Chen, C.; Yang, Y.; Song, Z.; Wormald, M. R.; Yu, C.; Rudd, P. M. Drug Discovery Today 2016, 21, 740.
[15]	(a) Meng, G.; Szostak, M. Org. Lett. 2015, 17, 4364.
	(b) Meng, G., Szostak, M. Org. Biomol. Chem. 2016, 14, 5690.
[16]	(a) Ye, D.; Liu, Z.; Chen, H.; Sessler, J. L.; Lei, C. Org. Lett. 2019, 21, 6888.
	(b) Ye, D.; Chen, H.; Liu, Z.; Lei, C. Chin. J. Org. Chem. 2021, 41, 1658 (in Chinese).
	(叶丹锋, 陈浩, 刘志园, 雷川虎, 有机化学, 2021, 41, 1658.) doi: 10.6023/cjoc202009048

叔丁醇锂催化N-苄基-N-叔丁氧羰基酰胺与糖的酯化反应

t-BuOLi Catalyzed Esterification of N-Benzyl-N-Boc-amides with Carbohydrates

RichHTML

PDF

Supporting Info.

Knowledge

Abstract

Cite this article

share this article

Fig. & Tab. 6

References 16

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	Zhaojin Yu, Zhan Zhang, Haiyang Wang, Bo Wang, Guangming Fu, Ying Zhang, Xiaopeng Yang, Aijun Dong, Xiaoming Ji. Study on Synthesis, Pyrolysis and Antioxidation of Ethyl Maltol Succinate Diester [J]. Chinese Journal of Organic Chemistry, 2024, 44(5): 1526-1534.
[2]	Yunhui Wan, Fumei Yang, Minghan Chen, Deli Sun, Danfeng Ye. Esterification of N-Benzyl-N-t-butoxycarbonyl-amides and Unsaturated Alcohol under Transition Metal-Free Conditions [J]. Chinese Journal of Organic Chemistry, 2024, 44(4): 1293-1300.
[3]	Mengfan Li, Xu Cheng. Chemoselective Electro-oxidation of Allyl Arene to Ester [J]. Chinese Journal of Organic Chemistry, 2024, 44(3): 1005-1012.
[4]	Yunzhe Zhong, Ying hen, Lei Yu, Hongwei Zhou. Electrochemical Mediated Esterification Reaction of Carboxylic Acids and Alcohols [J]. Chinese Journal of Organic Chemistry, 2023, 43(8): 2855-2863.
[5]	Yijun Shi, Xinyue Sun, Han Cao, Fusheng Bie, Jie Ma, Zhe Liu, Xingshun Cong. Thioesterification of Esters with Primary Aliphatic Thiols at Room Temperature [J]. Chinese Journal of Organic Chemistry, 2023, 43(7): 2499-2505.
[6]	Zehui Li, Haoyu Zou, Lincai Li, Yiling Zhao, Hongping Zhu. Synthesis and Propylene Oxide Carbonylation Hydroesterification Catalytic Property of N,O-Ligand Coordination Cobalt Compounds [J]. Chinese Journal of Organic Chemistry, 2023, 43(11): 3907-3915.
[7]	Peng Wang, Da Yang, Huan Liu. Recent Advances on Carbonylation of 1,3-Dienes [J]. Chinese Journal of Organic Chemistry, 2021, 41(9): 3379-3389.
[8]	Liang Shao, Fan Yang, Weijia Li, Fei Yu. Design, Synthesis and Anti-influenza A Virus Evaluation of Oleanolic Acid C3-Glycoconjugates [J]. Chinese Journal of Organic Chemistry, 2021, 41(6): 2454-2466.
[9]	Danfeng Ye, Hao Chen, Zhiyuan Liu, Chuanhu Lei. Transamidation of N-Benzyl-N-Boc-amides under Transition Metal-Free and Base-Free Conditions [J]. Chinese Journal of Organic Chemistry, 2021, 41(4): 1658-1669.
[10]	Shiyan Cheng, Chuhong Ou, Hongmin Lin, Junsong Jia, Haitao Tang, Yingming Pan, Guobao Huang, Xiujin Meng. Electrochemically Mediated Esterification of Aromatic Aldehydes with Aliphatic Alcohols via Anodic Oxidation [J]. Chinese Journal of Organic Chemistry, 2021, 41(12): 4718-4724.
[11]	Yu Jieqiang, Jia Jun, Wang Xingwang. Synthesis of a Type of Linear β,γ-Unsaturated α-Keto Tryptophol Ester Compounds [J]. Chinese Journal of Organic Chemistry, 2020, 40(9): 2778-2787.
[12]	Ma Hongpeng, Bai Chaolumen, Bao Yongsheng. Nano-Gold Catalyzed Transesterification of (Hetero) aryl Esters with Alkyl Halides via C-O Activation [J]. Chin. J. Org. Chem., 2019, 39(3): 734-746.
[13]	Menggen qiqige, Wu Yun, Bao Yongsheng. Metal-Free Esterification of Aldehydes or Carboxylic Acids with Quaternary Ammonium Salts [J]. Chin. J. Org. Chem., 2018, 38(4): 902-911.
[14]	Ding Haixin, Li Chuang, Dong Xiangyou, Cao Banpen, Zhang Ning, Hong Sanguo, Xiao Qiang. First Total Synthesis of Marine Natural Nucleoside Kipukasin D [J]. Chin. J. Org. Chem., 2018, 38(12): 3351-3355.
[15]	Ju Lei, Ma Chunmei, Tang Mi, Wang Yanhui, Yu Xinhong, Ma Hongmei. N-Heterocyclic Carbene-Catalyzed Oxidative Esterification of Aldehydes: Facile Access to α-Acyloxyacetates and Cyanomethyl Esters [J]. Chin. J. Org. Chem., 2018, 38(11): 3056-3062.