叔丁醇钾促进的硒氰酸酯与腙反应合成硒缩醛

doi:10.6023/cjoc202106048

摘要/Abstract

以硒氰酸酯和腙为起始物, 在碱存在条件下实现了一系列硒缩醛类化合物的合成. 本方法对硒氰酸(杂)芳酯以及(杂)芳基、烷基等类型的腙都具有良好的底物适应性和优秀的官能团兼容性, 同时适合克级反应制备, 为硒缩醛类化合物的高效合成提供了一种实用的新策略.

关键词: 硒氰酸酯, 腙, 硒缩醛, 重排

A series of selenoacetals were synthesized from selenocyanates and hydrazones under base condition. (Hetero)aryl selenocyanate and (hetero)aryl, alkyl hydrazones can undergo the process successfully, and shows broad substrate scope and excellent functional group tolerance. This protocol is suitable for gram-scale preparation, providing an efficient and practical synthetic strategy toward selenoacetals.

Key words: selenocyanate, hydrazone, selenoacetal, rearrangement

引用此文

叶浩, 任婷婷, 吴新星. 叔丁醇钾促进的硒氰酸酯与腙反应合成硒缩醛[J]. 有机化学, 2021, 41(11): 4338-4346.

Hao Ye, Tingting Ren, Xinxing Wu. ^tBuOK-Promoted Reaction of Selenocyanates and Hydrazones for the Synthesis of Selenoacetals[J]. Chinese Journal of Organic Chemistry, 2021, 41(11): 4338-4346.

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

分享此文

图/表 6

图式1. 硒缩醛类化合物的合成

Scheme 1. Synthesis of selenoacetals

Entry	Base	Solvent	T/℃	Yield^b/%
1	K₂CO₃	Dioxane	90	34
2	Cs₂CO₃	Dioxane	90	26
3	KOH	Dioxane	90	Trace
4	^tBuOLi	Dioxane	90	59
5	^tBuONa	Dioxane	90	65
6	^tBuOK	Dioxane	90	69
7	Et₃N	Dioxane	90	Trace
8	^tBuOK	Toluene	90	73
9	^tBuOK	THF	60	56
10	^tBuOK	MeCN	80	87
11	^tBuOK	DCE	80	39
12	^tBuOK	DME	80	51
13	^tBuOK	DMF	100	Trace
14	^tBuOK	DMSO	100	Trace
15^c	^tBuOK	MeCN	80	74
16^d	^tBuOK	MeCN	80	89

表1. 反应条件优化a

Table 1. Optimization of reaction conditions

表2. 腙底物的范围a,b

Table 2. Scope of hydrazones

表3. 硒氰酸酯底物的范围a,b

Table 3. Scope of selenocyanates

表4. 脂肪腙底物的范围a,b

Table 4. Scope of alkylhydrazones

图式2. 克级反应合成硒缩醛3y

Scheme 2. Gram-scale synthesis of selenoacetal 3y

参考文献 17

[1]	Clive, D. L. J. Tetrahedron 1978, 34, 1049. doi: 10.1016/0040-4020(78)80135-5
[2]	(a) Rao, C. V.; Wang, C.-Q.; Simi, B.; Rodriguez, J. G.; Cooma, I.; El-Bayoumy, K.; Reddy, B. S. Cancer Res. 2001, 61, 3647. pmid: 16620795
	(b) Richie, J. P.; Kleinman, W.; Desai, D. H.; Das, A.; Amin, S. G.; Pinto, J. T.; El-Bayoumy, K. Chem.-Biol. Interact. 2006, 161, 93. pmid: 16620795
	(c) Anan, Y.; Kimura, M.; Hayashi, M.; Koike, R.; Ogra, Y. Chem. Res. Toxicol. 2015, 28, 1803. doi: 10.1021/acs.chemrestox.5b00254 pmid: 16620795
[3]	Dumont, W.; Krief, A. Angew. Chem., nt. Ed. 1977, 16, 540.
[4]	Clive, D. L. J.; Menchen, S. M. J. Org. Chem. 1979, 44, 1883. doi: 10.1021/jo01325a034
[5]	(a) Dong, T.; Nie, J.; Zhang, C. Tetrahedron 2018, 74, 5642. doi: 10.1016/j.tet.2018.08.001 pmid: 11710243
	(b) Yu, Y.; Zhou, Y.; Song, Z.; Liang, G. Org. Biomol. Chem. 2018, 16, 4958. doi: 10.1039/C8OB00948A pmid: 11710243
	(c) Marpna, I. D.; Wanniang, K.; Lipon, T. M.; Risuklang Shangpliang, O.; Myrboh, B. J. Org. Chem. 2021, 86, 1980. doi: 10.1021/acs.joc.0c02630 pmid: 11710243
	(d) Mugesh, G.; Du Mont, W.-W.; Sies, H. Chem. Rev. 2001, 101, 2125. pmid: 11710243
	(e) Wu, Y.; Tian, X.; Zhang, H.; Chen, R.; Cao, T. Chin. J. Org. Chem. 2020, 40, 1384. (in Chinese) doi: 10.6023/cjoc201910003 pmid: 11710243
	(吴燕, 田仙芝, 张海玲, 陈睿, 曹团武, 有机化学, 2020, 40, 1384.) doi: 10.6023/cjoc201910003 pmid: 11710243
[6]	(a) Bürger, M.; Röttger, S. H.; Loch, M. N.; Jones, P. G.; Werz, D. B. Org. Lett. 2020, 22, 5025. doi: 10.1021/acs.orglett.0c01582
	(b) Jacob, A.; Jones, P. G.; Werz, D. B. Org. Lett. 2020, 22, 8720. doi: 10.1021/acs.orglett.0c03329
	(c) Sun, M.; Xu, K.; Guo, B.; Zeng, C. Chin. J. Org. Chem. 2021, 41, 2302. (in Chinese) doi: 10.6023/cjoc202102002
	(孙名扬, 徐坤, 郭兵兵, 曾程初, 有机化学, 2021, 41, 2302.) doi: 10.6023/cjoc202102002
[7]	(a) Maity, P.; Paroi, B.; Ranu, B. C. Org. Lett. 2017, 19, 5748. doi: 10.1021/acs.orglett.7b02571
	(b) Zhu, Y.-S.; Xue, Y.; Liu, W.; Zhu, X.; Hao, X.-Q.; Song, M.-P. J. Org. Chem. 2020, 85, 9106. doi: 10.1021/acs.joc.0c01035
	(c) Wu, D.; Qiu, J.; Li, C.; Yuan, L.; Yin, H.; Chen, F.-X. J. Org. Chem. 2020, 85, 934. doi: 10.1021/acs.joc.9b02786
[8]	(a) Cao, Y.; Jiang, L.; Yi, W. Adv. Synth. Catal. 2019, 361, 4360. doi: 10.1002/adsc.v361.18
	(b) Pan, C.; Liu, P.; Wu, A.; Li, M.; Wen, L.; Guo, W. Chin. J. Org. Chem. 2020, 40, 2855. (in Chinese) doi: 10.6023/cjoc202004051
	(潘超, 刘鹏, 武安国, 李明, 文丽荣, 郭维斯, 有机化学, 2020, 40, 2855.) doi: 10.6023/cjoc202004051
	(c) Krief, A.; Dumont, W.; Delmotte, C. Angew. Chem., nt. Ed. 2000, 39, 1669.
	(d) Wang, J.; Zhou, X.; Fan, W.; Du, S. Acta Chim. Sinica 1992, 50, 504. (in Chinese)
	(王瑾, 周洵钧, 范伟强, 杜少斌, 化学学报, 1992, 50, 504.)
	(e) Zhao, H.-R.; Liu, M.-Q.; Zhao, X.-J. Acta Chim. Sinica 2007, 65, 2155. (in Chinese)
	(赵华绒, 刘曼琼, 赵新建, 化学学报, 2007, 65, 2155.)
	(f) Ge, Y.; Kong, J.; Yang, C.; Yang, Q.; Zhang, X. Chin. J. Org. Chem. 2020, 40, 1760. (in Chinese) doi: 10.6023/cjoc201912022
	(葛颜玉, 孔晶, 杨成根, 杨倩, 张旭, 有机化学, 2020, 40, 1760.) doi: 10.6023/cjoc201912022
[9]	(a) Zhang, Y.; Wang, J. Top. Curr. Chem. 2012, 327, 239. doi: 10.1007/128_2012_322 pmid: 22547357
	(b) Zhu, D.; Chen, L.; Fan, H.; Yao, Q.; Zhu, S. Chem. Soc. Rev. 2020, 49, 908. doi: 10.1039/C9CS00542K pmid: 22547357
	(c) Kaufman, G. M.; Cook, F. B.; Shechter, H.; Bayless, J. H.; Friedman, L. J. Am. Chem. Soc. 1967, 89, 5736. doi: 10.1021/ja00998a061 pmid: 22547357
[10]	(a) Barluenga, J.; Valdes, C. Angew. Chem., nt. Ed. 2011, 50, 7486. pmid: 21378917
	(b) Barluenga, J.; Moriel, P.; Valdes, C.; Aznar, F. Angew. Chem., nt. Ed. 2007, 46, 5587. pmid: 21378917
	(c) Barluenga, J.; Tomas-Gamasa, M.; Aznar, F.; Valdes, C. Nat. Chem. 2009, 1, 494. doi: 10.1038/nchem.328 pmid: 21378917
	(d) Barluenga, J.; Tomas-Gamasa, M.; Aznar, F.; Valdes, C. Angew. Chem., nt. Ed. 2010, 49, 4993. pmid: 21378917
[11]	(a) Xiao, Q.; Zhang, Y.; Wang, J. Acc. Chem. Res. 2013, 46, 236. doi: 10.1021/ar300101k
	(b) Liu, Z.; Wang, J. J. Org. Chem. 2013, 78, 10024. doi: 10.1021/jo401850q
	(c) Xia, Y.; Zhang, Y.; Wang, J. ACS Catal. 2013, 3, 2586. doi: 10.1021/cs4006666
	(d) Xia, Y.; Qiu, D.; Wang, J. Chem. Rev. 2017, 117, 13810. doi: 10.1021/acs.chemrev.7b00382
	(e) Zhou, Q.; Gao, Y.; Xiao, Y.; Yu, L.; Fu, Z.; Li, Z.; Wang, J. Polym. Chem. 2019, 10, 569. doi: 10.1039/C8PY01529E
	(f) Liu, Z.; Zhang, Y.; Wang, J. Chin. J. Org. Chem. 2013, 33, 687. (in Chinese) doi: 10.6023/cjoc201301023
	(刘振兴, 张艳, 王剑波, 有机化学, 2013, 33, 687.) doi: 10.6023/cjoc201301023
[12]	(a) Chen, Z.-S.; Duan, X.-H.; Wu, L.-Y.; Ali, S.; Ji, K.-G.; Zhou, P.-X.; Liu, X.-Y.; Liang, Y.-M. Chem.-Eur. J. 2011, 17, 6918. doi: 10.1002/chem.201100248
	(b) Wu, X.-X.; Shen, Y.; Chen, W.-L.; Chen, S.; Hao, X.-H.; Xia, Y.; Xu, P.-F.; Liang, Y.-M. Chem. Commun. 2015, 51, 8031. doi: 10.1039/C5CC02246K
	(c) Ye, Y.-Y.; Zhou, P.-X.; Luo, J.-Y.; Zhong, M.-J.; Liang, Y.-M. Chem. Commun. 2013, 49, 10190. doi: 10.1039/c3cc45583a
	(d) Zhou, P.-X.; Ye, Y.-Y.; Liang, Y.-M. Org. Lett. 2013, 15, 5080. doi: 10.1021/ol402457h
[13]	(a) Ren, X.; Zhu, L.; Yu, Y.; Wang, Z.-X.; Huang, X. Org. Lett. 2020, 22, 3251. doi: 10.1021/acs.orglett.0c01040
	(b) Zhu, L.; Ren, X.; Yu, Y.; Ou, P.; Wang, Z.-X.; Huang, X. Org. Lett. 2020, 22, 2087. doi: 10.1021/acs.orglett.0c00579
[14]	(a) Feng, J.; Li, B.; He, Y.; Gu, Z. Angew. Chem., nt. Ed. 2016, 55, 2186.
	(b) Chen, H.; Huang, L.; Fu, W.; Liu, X.; Jiang, H. Chem.-Eur. J. 2012, 18, 10497. doi: 10.1002/chem.v18.34
	(c) Zhou, F.; Ding, K.; Cai, Q. Chem.-Eur. J. 2011, 17, 12268. doi: 10.1002/chem.v17.44
	(d) Xu, K.; Shen, C.; Shan, S. Chin. J. Org. Chem. 2015, 35, 294. (in Chinese) doi: 10.6023/cjoc201409034
	(许恺, 沈冲, 单尚, 有机化学, 2015, 35, 294.) doi: 10.6023/cjoc201409034
[15]	(a) Bamford, W. R.; Stevens, T. S. J. Chem. Soc. 1952, 4735.
	(b) Arunprasath, D.; Sekar, G. Adv. Synth. Catal. 2017, 359, 698. doi: 10.1002/adsc.v359.4
[16]	(a) Harusawa, S.; Yoneda, R.; Omori, Y.; Kurihara, T. Tetrahedron Lett. 1987, 28, 4189.
	(b) Wang, Z.-H.; Ji, X.-M.; Hu, M.-L.; Tang, R.-Y. Tetrahedron Lett. 2015, 56, 5067.
[17]	Fulton, J. R.; Aggarwal, V. K.; de Vicente, J. Eur. J. Org. Chem. 2005, 1479.