Morita-Baylis-Hillman加合物和N-羟基邻苯二甲酰亚胺的电化学烯丙基烷基化形成C(sp3)—C(sp3)键

doi:10.6023/cjoc202209024

有机化学 ›› 2023, Vol. 43 ›› Issue (4): 1574-1583.DOI: 10.6023/cjoc202209024 上一篇下一篇

研究论文

Morita-Baylis-Hillman加合物和N-羟基邻苯二甲酰亚胺的电化学烯丙基烷基化形成C(sp³)—C(sp³)键

孙丽^a, 宋国欣^a, 韩家乐^a, 李继玉^a, 赵月^a, 杨璐华^a, 张峰^a, 赵坤^b, 毛比明^a^,^*()

a 山东第一医科大学(山东省医学科学院)药学与制药科学学院(药物研究所) 济南 250117
b 山东大学药学院天然产物化学生物学教育部重点实验室济南 250012

收稿日期:2022-09-19 修回日期:2022-10-19 发布日期:2022-11-15
通讯作者: 毛比明
基金资助:
国家自然科学基金(22101156); 国家自然科学基金(22101154); 山东省自然科学基金(ZR2021QB032); 山东省自然科学基金(ZR2021QB038); 泰山学者工程专项经费资助项目

Electrochemical Allylic Alkylation of Morita-Baylis-Hillman Adducts and N-Hydroxyphthalimide Esters towards C(sp³)—C(sp³) Bond Formation

Li Sun^a, Guoxin Song^a, Jiale Han^a, Jiyu Li^a, Yue Zhao^a, Luhua Yang^a, Feng Zhang^a, Kun Zhao^b, Biming Mao^a()

a School of Parmacy and Pharmaceutical Science & Institute of Materia Medica, Shandong First Medical University & Shandong Academy of Medical Sciences, Jinan 250117
b Key Laboratory of Chemical Biology (Ministry of Education), School of Pharmaceutical Sciences, Shandong University, Jinan 250012

Received:2022-09-19 Revised:2022-10-19 Published:2022-11-15
Contact: Biming Mao
Supported by:
National Natural Science Foundation of China(22101156); National Natural Science Foundation of China(22101154); Natural Science Foundation of Shandong Province(ZR2021QB032); Natural Science Foundation of Shandong Province(ZR2021QB038); Taishan Scholar Youth Program of Shandong Province

文章分享

1. 231574S.pdf.pdf(3858KB)

摘要/Abstract

报道了一种无外加氧化还原剂、电还原方法, 使Morita-Baylis-Hillman (MBH)加合物实现烯丙基烷基化. 这种转变的一个关键特征是, 既不需要外部化学还原剂也不需要金属催化剂. N-烷酰氧基邻苯二甲酰亚胺(NHP)酯通过电子还原产生烷基自由基, 在烷基化过程中以高立体选择性和区域选择性展示出对烯烃取代的广泛官能团耐受性.

关键词: 烯丙基烷基化, Morita-Baylis-Hillman (MBH)加合物, 电化学还原路径

A redox-free, electroreductive approach to achieve allylic alkylation by employing Morita-Baylis-Hillman (MBH) adducts is reported. A critical feature of this transformation is that neither external chemical oxidants nor metal catalysts are required. Alkyl radical produced by electron reduction with N-hydroxyphthalimide (NHP) esters, displaying broad tolerance of functional groups and alkene substitution patterns in high stereoselectivity and regioselectivity.

Key words: allylic alkylation, Morita-Baylis-Hillman (MBH) adducts, electroreductive approach

引用此文

孙丽, 宋国欣, 韩家乐, 李继玉, 赵月, 杨璐华, 张峰, 赵坤, 毛比明. Morita-Baylis-Hillman加合物和N-羟基邻苯二甲酰亚胺的电化学烯丙基烷基化形成C(sp³)—C(sp³)键[J]. 有机化学, 2023, 43(4): 1574-1583.

Li Sun, Guoxin Song, Jiale Han, Jiyu Li, Yue Zhao, Luhua Yang, Feng Zhang, Kun Zhao, Biming Mao. Electrochemical Allylic Alkylation of Morita-Baylis-Hillman Adducts and N-Hydroxyphthalimide Esters towards C(sp³)—C(sp³) Bond Formation[J]. Chinese Journal of Organic Chemistry, 2023, 43(4): 1574-1583.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

图/表 7

Scheme 1. Protocol for allylic alkylation of Morita-Baylis-Hill- man (MBH) adducts

Entry		Variation from condition^a	Yield^b/%
1		None	90
2		CH₃CN instead of DMF	77
3		DMSO instead of DMF	48
4	ⁿBu₄NBF₄ instead of ⁿBu₄NHSO₄		67
5		Pt (－) instead of C (－)	41
6		Fe (－) instead of C (－)	43
7		Pt (+) instead of C (+)	58
8		I=4 mA, 135 min	88
9		I=8 mA, 68 min	72
10		1a 0.15 mmol	72
11		Boc instead of Ac	89
12		Air instead of Ar	67
13		No electric current	N.D.

Table 1. Effects of reaction parameters

Table 2. Substrate scope of the reactiona

Table 3. Substrate scope of the reactiona

Scheme 2. Gram-scale reaction and radical trapping experiments

Figure 1. Cyclic voltammograms of substrates 1a, 2a

Scheme 3. Proposed reaction mechanism

参考文献 13

[1]	For selected reviews, see: (a) Basavaiah, D.; Reddy, B. S.; Badsara,, S. S. Chem. Rev. 2010, 110, 5447. doi: 10.1021/cr900291g pmid: 12630854
	(b) Singh, V.; Batra, S. Tetrahedron 2008, 64, 4511. doi: 10.1016/j.tet.2008.02.087 pmid: 12630854
	(c) Declerck, V.; Martinez, J.; Lamaty, F. Chem. Rev. 2009, 109, 1. doi: 10.1021/cr068057c pmid: 12630854
	(d) Ma, G.-N.; Jiang, J.-J.; Shi, M.; Wei, Y. Chem. Commun. 2009, 5496. pmid: 12630854
	(e) Trost, B. M.; Machacek, M. R.; Aponick, A. Acc. Chem. Res. 2006, 39, 747. doi: 10.1021/ar040063c pmid: 12630854
	(f) Belda, O.; Moberg, C. Acc. Chem. Res. 2004, 37, 159. doi: 10.1021/ar030239v pmid: 12630854
	(g) Basavaiah, D.; Rao, A. J.; Satyanarayana, T. Chem. Rev. 2003, 103, 811. pmid: 12630854
	(h) Trost, B. M.; Van Vranken, D. L. Chem. Rev. 1996, 96, 395. doi: 10.1021/cr9409804 pmid: 12630854
[2]	For selected examples, see: (a) Hu, Z.; Cui, H.; Jiang, K.; Chen,, Y. Sci. China: Chem. 2009, 52, 1309. pmid: 19707668
	(b) Feng, X.; Yuan, Y.-Q.; Cui, H.-L.; Jiang, K.; Chen, Y.-C. Org. Biomol. Chem. 2009, 7, 3660. doi: 10.1039/b912110b pmid: 19707668
	(c) Trost, B. M.; Brennan, M. K. Org. Lett. 2007, 9, 3961. doi: 10.1021/ol701585b pmid: 19707668
	(d) Trost, B. M.; Tsui, H.-C.; Toste, F. D. J. Am. Chem. Soc. 2000, 122, 3534. doi: 10.1021/ja994326n pmid: 19707668
[3]	For selected examples, see: (a) Yao, L.; Wang, C.-J. Adv. Synth. Catal. 2015, 357, 384. doi: 10.1002/adsc.201400790
	(b) Chen, L.-Y.; Yu, X.-Y.; Chen, J.-R.; Feng, B.; Zhang, H.; Qi, Y.-H.; Xiao, W.-J. Org. Lett. 2015, 17, 1381. doi: 10.1021/acs.orglett.5b00077
	(c) Zhan, G.; Zhou, Q.-Q.; Du, W.; Chen, Y.-C. Synthesis 2014, 3383.
	(d) Huang, J.-R.; Cui, H.-L.; Lei, J.; Sun, X.-H.; Chen, Y.-C. Chem. Commun. 2011, 47, 4784. doi: 10.1039/c0cc05616b
	(e) Cui, H.-L.; Feng, X.; Peng, J.; Lei, J.; Jiang, K.; Chen, Y.-C. Angew. Chem., Int. Ed. 2009, 48, 5737. doi: 10.1002/anie.v48:31
[4]	(a) Hong, L.; Sun, W.; Liu, C.; Zhao, D.; Wang, R. Chem. Commun. 2010, 46, 2856. doi: 10.1039/b926037d
	(b) Sun, W.; Hong, L.; Liu, C.; Wang, R. Org. Lett. 2010, 12, 3914. doi: 10.1021/ol101601d
[5]	(a) Liu, X.-W.; Han, W.-Y.; Liu, X.-L.; Zhou, Y.; Zhang, X.-M.; Yuan, W.-C. Tetrahedron 2014, 70, 9191. doi: 10.1016/j.tet.2014.10.031 pmid: 24661847
	(b) Santhoshi, A.; Mahendar, B.; Mattapally, S.; Sadhu, P. S.; Banerjee, S. K.; Rao, J. V. Bioorg. Med. Chem. Lett. 2014, 24, 1952. doi: 10.1016/j.bmcl.2014.02.073 pmid: 24661847
	(c) Lin, A.; Mao, H.; Zhu, X.; Ge, H.; Tan, R.; Zhu, C.; Cheng, Y. Adv. Synth. Catal. 2011, 353, 3301. doi: 10.1002/adsc.201100522 pmid: 24661847
	(d) Han, E.-G.; Kim, H. J.; Lee, K.-J. Tetrahedron 2009, 65, 9616. doi: 10.1016/j.tet.2009.09.047 pmid: 24661847
[6]	For selected examples, see: (a) Zhao, S.; Zhao, Y.-Y.; Lin, J.-B.; Xie, T.; Liang, Y.-M.; Xu,, P.-F. Org. Lett. 2015, 17, 3206. doi: 10.1021/acs.orglett.5b01066
	(b) Tong, G.; Zhu, B.; Lee, R.; Yang, W.; Tan, D.; Yang, C.; Han, Z.; Yan, L.; Huang, K.-W.; Jiang, Z. J. Org. Chem. 2013, 78, 5067. doi: 10.1021/jo400496z
	(c) Chen, G.-Y.; Zhong, F.; Lu, Y. ; Org. Lett. 2012, 14, 3955. doi: 10.1021/ol301962e
	(d) Liu, C.; Tan, B.-X.; Jin, J.-L.; Zhang, Y.-Y.; Dong, N.; Li, X.; Cheng, J.-P. J. Org. Chem. 2011, 76, 5838. doi: 10.1021/jo200557b
	(e) Cui, H.-L.; Huang, J.-R.; Lei, J.; Wang, Z.-F.; Chen, S.; Wu, L.; Chen, Y.-C. Org. Lett. 2010, 12, 720. doi: 10.1021/ol100014m
	(f) Jiang, K.; Peng, J.; Cui, H.-L.; Chen, Y.-C. Chem. Commun. 2009, 3955.
	(g) Cui, H.-L.; Peng, J.; Feng, X.; Du, W.; Jiang, K.; Chen, Y.-C. Chem. Eur. J. 2009, 15, 1574. doi: 10.1002/chem.v15:7
	(h) Jiang, Y.-Q.; Shi, Y.-L.; Shi, M. J. Am. Chem. Soc. 2008, 130, 7202. doi: 10.1021/ja802422d
	(i) Cho, C.-W.; Krische, M. J. Angew. Chem., Int. Ed. 2004, 43, 6689. doi: 10.1002/(ISSN)1521-3773
[7]	(a) Yadav, A. K.; Sharma, A. K.; Singh, K. N. Org. Chem. Front. 2019, 6, 989. doi: 10.1039/C9QO00166B pmid: 18426237
	(b) Dai, X.; Cheng, D.; Guan, B.; Mao, W.; Xu, X.; Li, X. J. Org. Chem. 2014, 79, 7212. doi: 10.1021/jo501097b pmid: 18426237
	(c) Zhao, H.; Ni, N.; Li, X.; Cheng, D.; Xu, X. Tetrahedron Lett. 2021, 65, 152746. doi: 10.1016/j.tetlet.2020.152746 pmid: 18426237
	(d) Lebargy, C.; Schutter, C.De; Legay, R.; Pfund, E.; Lequeux, V. Synlett 2018, 29, 46. doi: 10.1055/s-0036-1590922 pmid: 18426237
	(e) Mandal, S. K.; Paira, M.; Roy, S. C. J. Org. Chem. 2008, 73, 3823. doi: 10.1021/jo800049p pmid: 18426237
[8]	(a) Paria, S.; Carletti, E.; Marcon, M.; Cherubini-Celli, A.; Mazzanti, A.; Rancan, M.; Dell’Amico, L.; Bonchio, M.; Companyo, X. J. Org. Chem. 2020, 85, 4463. doi: 10.1021/acs.joc.0c00175 pmid: 32081000
	(b) Bai, X.; Qian, L.; Zhang, H.-H.; Yu, S. Org. Lett. 2021, 23, 8322. doi: 10.1021/acs.orglett.1c03064 pmid: 32081000
[9]	(a) Siu, J. C.; Fu, N.; Lin, S. Acc Chem. Res. 2020, 53, 547. doi: 10.1021/acs.accounts.9b00529 pmid: 35700274
	(b) Yuan, Y.; Yang, J.; Lei, A. Chem. Soc. Rev. 2021, 50, 10058. doi: 10.1039/D1CS00150G pmid: 35700274
	(c) Yoshida, J. I.; Shimizu, A.; Hayashi, R. Chem. Rev. 2018, 118, 4702. doi: 10.1021/acs.chemrev.7b00475 pmid: 35700274
	(d) Francke, R.; Little, R. D. Chem. Soc. Rev. 2014, 43, 2492. doi: 10.1039/c3cs60464k pmid: 35700274
	(e) Huang, Y.-Q.; Wu, Z.-J.; Zhu, L.; Gu, Q.; Lu, X.; You, S.-L.; Mei, T.-S. CCS Chem. 2021, 3, 3501. pmid: 35700274
	(f) Xiong, P.; Hemming, M.; Ivlev, S. I.; Meggers, E. J. Am. Chem. Soc. 2022, 144, 6964. doi: 10.1021/jacs.2c01686 pmid: 35700274
	(g) Go, S. Y.; Chung, H.; Shin, S. J.; An, S.; Youn, J. H.; Im, T. Y.; Kim, J. Y.; Chung, T. D.; Lee, H. G. J. Am. Chem. Soc. 2022, 144, 9149. doi: 10.1021/jacs.2c03213 pmid: 35700274
	(h) Chen, W.; Ni, S.; Wang, Y.; Pan, Y. Org. lett. 2022, 24, 3647. doi: 10.1021/acs.orglett.2c01247 pmid: 35700274
	(i) Kong, X.; Chen, Y.; Chen, X.; Lu, Z. X.; Wang, W.; Ni, S. F.; Cao, Z. Y. Org. Lett. 2022, 24, 2137. doi: 10.1021/acs.orglett.2c00408 pmid: 35700274
	(j) Niu, L.; Jiang, C.; Liang, Y.; Liu, D.; Bu, F.; Shi, R.; Chen, H.; Chowdhury, A. D.; Lei, A. J. Am. Chem. Soc. 2020, 142, 17693. doi: 10.1021/jacs.0c08437 pmid: 35700274
	(k) Bertuzzi, G.; Ombrosi, G.; Bandini, M. Org. lett. 2022, 24, 4354. doi: 10.1021/acs.orglett.2c01529 pmid: 35700274
[10]	(a) Chen, M.; Wu, Z. J.; Song, J.; Xu, H. C. Angew. Chem., Int. Ed. 2022, 61, e202115954. pmid: 33231074
	(b) Cai, C.Y.; Wu, Z.J.; Liu, J.Y.; Chen, M.; Song, J.; Xu, H.C. Nat. Commun. 2021, 12, 3745. doi: 10.1038/s41467-021-24125-5 pmid: 33231074
	(c) Lu, L.; Siu, J.; Lai, Y.; Lin, S. J. Am. Chem. Soc. 2020, 142, 21272. doi: 10.1021/jacs.0c10899 pmid: 33231074
	(d) Zhang, W.; Lin, S. J. Am. Chem. Soc. 2020, 142, 20661. doi: 10.1021/jacs.0c08532 pmid: 33231074
	(e) He, M.; Mo, Z.; Wang, Z.; Cheng, S.; Xie, R.; Tang, H.; Pan, Y. Org. Lett. 2020, 22, 714. doi: 10.1021/acs.orglett.9b04546 pmid: 33231074
	(f) He, M.; Yao, Y.; Ai, C.; Mo, Z.; Wu, Y.; Zhou, Q.; Pan, Y.; Tang, H. Org. Chem. Front. 2022, 9, 781. doi: 10.1039/D1QO01458G pmid: 33231074
	(g) Liu, H.; He, M.; Tang, H. Org. Chem. Front. 2022, 9, 5955. doi: 10.1039/D2QO01281B pmid: 33231074
[11]	(a) Liu, Y.; Xue, L.; Shi, B.; Bu, F.; Wang, D.; Lu, L.; Shi, R.; Lei, A. Chem. Commun. 2019, 55, 14922. doi: 10.1039/C9CC08528A
	(b) Niu, K.; Song, L.; Hao, Y.; Liu, Y.; Wang, Q. Chem. Commun. 2020, 56, 11673. doi: 10.1039/D0CC05391K
	(c) Chen, X.; Luo, X.; Peng, X.; Guo, J.; Zai, J.; Wang, P. Chem. Eur. J. 2020, 26, 3226. doi: 10.1002/chem.v26.15
[12]	When this manuscript was in preparation for submission, an electrochemical alkylation of MBH adducts with redox-active esters as radical precursors was reported; see: Bertuzzi, G.; Ombrosi, G.; Bandini, M. Org. Lett. 2022, 24, 4354. doi: 10.1021/acs.orglett.2c01529 pmid: 35700274
[13]	(a) Wang, D.; Wan, Z.; Zhang, H.; Alhumade, H.; Yi, H.; Lei, A. ChemSusChem 2021, 14, 5399. doi: 10.1002/cssc.v14.24
	(b) Xu, L.; Ma, Z.; Hu, X.; Zhang, X.; Gao, S.; Liang, D.; Wang, B.; Li, W.; Li, Y. Org. Biomol. Chem. 2022, 20, 1013. doi: 10.1039/D1OB02379A

Morita-Baylis-Hillman加合物和N-羟基邻苯二甲酰亚胺的电化学烯丙基烷基化形成C(sp³)—C(sp³)键

Electrochemical Allylic Alkylation of Morita-Baylis-Hillman Adducts and N-Hydroxyphthalimide Esters towards C(sp³)—C(sp³) Bond Formation

RichHTML

PDF

补充材料