对甲苯亚磺酸钠/KI介导端炔的需氧氧化碘代反应合成1-碘代炔和1,3-二炔

doi:10.6023/cjoc202007031

有机化学 ›› 2021, Vol. 41 ›› Issue (1): 394-399.DOI: 10.6023/cjoc202007031 上一篇下一篇

研究论文

对甲苯亚磺酸钠/KI介导端炔的需氧氧化碘代反应合成1-碘代炔和1,3-二炔

周鹏^a^,^*(), 冯尚伟^a, 邱会华^a, 张建涛^a^,^*()

a 广东石油化工学院化学学院广东茂名 525000

收稿日期:2020-07-09 修回日期:2020-09-11 发布日期:2020-10-12
通讯作者: 周鹏, 张建涛
作者简介:
* Corresponding author. E-mail: zzd83@aliyun.com; 1351248781@qq.com
基金资助:
国家自然科学基金(21602035); 广东省自然科学基金(2016A030307030); 广东石油化工学院创新研究团队(519124)

Sodiump-Toluenesulfinate/KI-Mediated Aerobic Oxidative Iodination of Terminal Alkynes for Synthesis of 1-Iodoalkynes and 1,3-Diynes

Peng Zhou^a^,^*(), Shangwei Feng^a, Huihua Qiu^a, Jiantao Zhang^a^,^*()

a College of Chemistry, Guangdong University of Petrochemical Technology, Maoming, Guangdong 525000

Received:2020-07-09 Revised:2020-09-11 Published:2020-10-12
Contact: Peng Zhou, Jiantao Zhang
Supported by:
the National Natural Science Foundation of China(21602035); the Natural Science Foundation of Guangdong Province(2016A030307030); the Program for Innovative Research Team of Guangdong University of Petrochemical Technology(519124)

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摘要/Abstract

基于对甲苯亚磺酸钠/KI介导端炔的需氧氧化碘代反应, 发展了一种高效合成1-碘代炔的绿色环保方法. 该方法以最绿色环保的空气作为氧化剂, 无需其他有毒的氧化剂, 具有效率高、反应操作简单、底物适用性广、试剂绿色环保和反应条件温和的特点. 此外, 基于对甲苯亚磺酸钠/KI介导端炔的需氧氧化碘代反应, 发展了一种一锅法无金属催化端炔合成对称1,3-二炔的方法.

关键词: 端炔, 1-碘代炔, 空气, 亚磺酸钠, 1,-二炔

A practical and environmentally friendly protocol for the synthesis of 1-iodoalkynes was developed via sodium sulfinate-KI mediated aerobic oxidative iodination of terminal alkynes. This transformation features simple operation, high efficiency, broad functional-group tolerance and mild reaction conditions. Especially, dioxygen was used in these reactions which avoided the addition of hazardous or toxic oxidants. Moreover, for the purpose of increasing the synthetic utility of this method, an efficient transition-metal-free synthetic approach to symmetrical 1,3-diynes was developed via the iodination/ homocoupling of terminal alkynes in a one-pot manner.

Key words: terminal alkyne, 1-iodoalkyne, air, sodium sulfinate, 1,3-diyne

引用此文

周鹏, 冯尚伟, 邱会华, 张建涛. 对甲苯亚磺酸钠/KI介导端炔的需氧氧化碘代反应合成1-碘代炔和1,3-二炔[J]. 有机化学, 2021, 41(1): 394-399.

Peng Zhou, Shangwei Feng, Huihua Qiu, Jiantao Zhang. Sodiump-Toluenesulfinate/KI-Mediated Aerobic Oxidative Iodination of Terminal Alkynes for Synthesis of 1-Iodoalkynes and 1,3-Diynes[J]. Chinese Journal of Organic Chemistry, 2021, 41(1): 394-399.

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参考文献 18

[1]	Selected reviews on the application of 1-iodoalkynes: (a) Brand, J. P.; Waser, J. Chem. Soc. Rev. 2012, 41, 4165.
	Wu, W.; Jiang, H. Acc. Chem. Res. 2014, 47, 2483.
	Shi, W.; Lei, A. Tetrahedron Lett. 2014, 55, 2763.
	Danilkina, N.A.; Govdi, A.I.; Balova, I.A. Synthesis 2020, 52, 1874.
[2]	Kabalka, G.W.; Mereddy, A.R. J. Labelled Compd. Radiopharm. 2005, 48, 359.
	Ferris, T.; Carroll, L; Mease, R.C.; Spivey, A.C.; Aboagye, E.O. Tetrahedron Lett. 2019, 60, 936.
	Dubost, E.; McErlain, H.; Babin, V.; Sutherland, A.; Cailly, T. J. Org. Chem. 2020, 85, 8300.
[3]	Mandai, T.; Matsumoto, T.; Kawada, M.; Tsuji, J. J. Org. Chem. 1992, 57, 6090.
	Nishikawa, T.; Shibuya, S.; Hosokawa, S.; Isobe, M. Synlett 1994, 485.
	Naskar, D.; Roy, S. J. Org. Chem. 1999, 64, 6896.
	Blackmore, I.J.; Boa, A.N.; Murray, E.J.; Dennis, M.; Woodward, S. Tetrahedron Lett. 1999, 40, 6671.
	Luithle, J.E.; Pietruszka, J. Eur. J. Org. Chem. 2000, 2557.
	Das, J.P.; Roy, S. J. Org. Chem. 2002, 67, 7861.
	Kabalka, G.W.; Mereddy, A.R. Tetrahedron 2004, 45, 1417.
	Starkov, P.; Rota, F.; D’Oyley, J.M.; Sheppard, T.D. Adv. Synth. Catal. 2012, 354, 3217.
	Pelletier, G.; Lie, S.; Mousseau, J.J.; Charette, A.B. Org. Lett. 2012, 14, 5464.
[4]	Heasley, V.L.; Shellhamer, D.F.; Heasley, L.E.; Yaeger, D.B. J. Org. Chem. 1980, 45, 4649.
	Chen, S.-N.; Hung, T.-T.; Lin, T.-C.; Tsai, F.-Y. J. Chin. Chem. Soc. 2009, 56, 1078.
	Rao, M.L.N.; Periasamy, M. Synth. Commun. 1995, 25, 2295.
	He, G.-W.; Liu, F.-W.; Xu, X.-H. Chin. J. Org. Chem. 2007, 27, 663. (in Chinese)
	(贺干武, 刘凤伟, 许新华, 有机化学, 2007, 27, 663.).
	Meng, L.-G.; Cai, P.-J.; Guo, Q.-X.; Xue, S. Synth. Commun. 2008, 38, 225.
	Xia, Z.; Corcé , V.; Zhao, F.; Przybylski, C.; Espagne, A.; Jullien, L; Saux, T.L.; Gimbert, Y.; Dossmann, H.; Mouriès-Mansuy, V.; Ollivier , C.; Louis Fensterbank, L.Nat. Chem. 2019, 11, 797.
[5]	Yan, J.; Li, J.; Cheng, D. Synlett 2007, 15, 2442.
	Li, Y.; Huang, D.; Wang, D.; Huang, J.; Maruoka, K. CN 106831283, 2020.
[6]	Naskar, D.; Roy, S. J. Org. Chem. 1999, 64, 6896.
	Hein, J.E.; Tripp, J.C.; Krasnova, L.B.; Sharpless, B.; Fokin, V.V. Angew. Chem., Int. Ed. 2009, 48, 8018.
	Nçsel, P.; Lauterbach, T.; Rudolph, M.; Rominger, F.; Hashmi, A.S.K. Chem.-Eur. J. 2013, 19, 8634.
	Wang, B.; Zhang, J.; Wang, X.; Liu, N.; Chen, W.; Hu, Y. J. Org. Chem. 2013, 78, 10519.
	Li, M.; Li, Y.; Zhao, B.; Liang, F.; Jin, L.-Y. RSC Adv. 2014, 4, 30046.
	Gómez-Herrera, A.; Nahra, F.; Brill, M.; Nolan, S.P.; Cazin, C.S.J. ChemCatChem 2016, 8, 3381.
	Shi, W.; Guan, Z.; Cai, P.; Chen, H. J. Catal. 2017, 353, 199.
	Yao, M.; Zhang, J.; Yang, S.; Xiong, H.; Li, L.; Liu, E; Shi, H. RSC Adv. 2020, 10, 3946.
	Yao, M.; Zhang, J.; Yang, S.; Liu, E.; Xiong, H. Synlett 2020, 31, 1102.
[7]	Brunel Y. ; Rousseau, G. Tetrahedron Lett . 1995 , 36 , 2619.
[8]	Nouzarian, M. ; Hosseinzadeh, R. ; Golchoubian, H. Synth. Commun . 2013 , 43 , 2913.
[9]	Rao, D.S. ; Reddy, T.P. ; Kashyap, S. Org. Biomol. Chem . 2018 , 16 , 1508.
[10]	Nishiguchi, I. ; Kanbe, O. ; Itoh, K. ; Maekawa, H. Synlett 2000 , 89.
[11]	Casarini, A.; Dembech, P.; Reginato, G.; Ricci, A.; Seconi, G. Tetrahedron Lett. 1991, 32, 2169.
	Reddy, K.R.; Venkateshwar, M.; Maheswari, C.U.; Kumar, P.S. Tetrahedron Lett. 2010, 51, 2170.
	Liu, Y.; Huang, D.; Huang, J.; Maruoka, K. J. Org. Chem. 2017, 82, 11865.
	Srujana, K.; Swamy, P.; Naresh, M.; Durgaiah, C.; Rammurthy, B.; Sai, G.K.; Sony, T.; Narender, N. ChemistrySelect 2017, 2, 748.
	Liu, X.; Chen, G.; Li, C.; Liu, P. Synlett 2018, 29, 2051.
	Chen, S.; Zhang, X.; Zhao, H.; Guo, X.; Hu, X. Chin. J. Org. Chem. 2018, 38, 1172. (in Chinese)
	(陈锁, 章晓炜, 赵辉, 郭晓红, 胡祥国, 有机化学, 2018, 38, 1172.).
[12]	Selected examples: (a) Lv, Y.; Li, Y.; Xiong, T.; Lu, Y.; Liu, Q.; Zhang, Q. Chem. Commun. 2014, 50, 2367.
	Tan, C.; Liu, Y.; Liu, X.; Jia, H.; Xu, K.; Huang, S.; Wang, J.; Tan, J. Org. Chem. Front. 2020, 7, 780.
	Quan, J.; He, X.; Yan, X.; Li, X.; Xu, X. Chin. J. Org. Chem. 2020, 40, 1033. (in Chinese)
	(全积宁, 何小雪, 严新焕, 李小青, 许响生, 有机化学, 2020, 40, 1033.).
	Lv, Y.; Sun, K.; Wang, T.; Li, G.; Pu, W.; Chai, N.; Shen, H.; Wu, Y. RSC Adv. 2015, 5, 72142.
	Huang, L.; Yin, W.; Wang, J.; Gan, C.; Huang, Y.; Huang, C.; He, Y. RSC Adv. 2019, 9, 2381.
	Yuan, J.; Ma, X.; Yi, H.; Liu, C.; Lei, A. Chem. Commun. 2014, 50, 14386.
	Wu, X.-F.; Gong, J.-L.; Qi, X. Org. Biomol. Chem. 2014, 12, 5807.
[13]	Zhou, P.; Qiu, H.; Shi, J. Chin. J. Org. Chem. 2016, 36, 425. (in Chinese)
	(周鹏, 邱会华, 施继成, 有机化学, 2016, 36, 425.).
	Qiu, H.; Cheng, B.; Huang, Y.; Chen, C.; Zhou, P. Chin. J. Org. Chem. 2018, 38, 1817. (in Chinese)
	(邱会华, 成博睿, 黄颖思, 陈翠, 周鹏, 有机化学, 2018, 38, 1817.).
	Zhou, P.; Pan, Y.; Tan, H.; Liu, W. J. Org. Chem. 2019, 84, 15662.
	Qiu, H.; Zhou, P.; Liu, W.; Zhang, J.; Chen, B. ChemistrySelect 2020, 5, 2935.
[14]	Chen, Z. ; Jiang, H. ; Wang, A. ; Yang, S. J. Org. Chem . 2010 , 75 , 6700.
[15]	Meesin, J. ; Katrun, P. ; Pareseecharoen, C. ; Pohmakotr, M ; Reutrakul, V. ; Soorukram, D. ; Kuhakarn, C. J. Org. Chem . 2016 , 81 , 2744.
[16]	Recent reviews on radical transformations of alkynes: (a) Xu J.; Song, Q. Chin. J. Org. Chem. 2016, 36, 1151. (in Chinese)
	(许健, 宋秋玲, 有机化学, 2016, 36, 1151.).
	Huang, M.-H.; Hao, W.-J.; Li, G.; Tu, S.-J.; Jiang, B. Chem. Commun. 2018, 54, 10791.
	Guerrero-Robles, M.A.; Vilchis-Reyes, M.A.; Ramos-Rivera, E.M.; Alvarado, C. ChemistrySelect 2019, 4, 13698.
[17]	Selected examples on the transformation via TolSI: (a) Katrun, P.; Chiampanichayakul, S.; Korworapan, K.; Pohmakotr, M.; Reutrakul, V.; Jaipetch, T.; Kuhakarn, C.Eur. J. Org. Chem. 2010, 5633.
	Buathongjan, C.; Beukeaw, D.; Yotphan, S. Eur. J. Org. Chem. 2015, 1575.
	Wei, W.; Liu, C.; Yang, D.; Wen, J.; You, J.; Wang, H. Adv. Synth. Catal. 2015, 357, 987.
	Jiang, Y.-Y.; Wang, Q.-Q.; Liang, S.; Hu, L.-M.; Little, R.D.; Zeng, C.-C. J. Org. Chem. 2016, 81, 4713.
	Lai, J.; Chang, L.; Yuan, G. Org. Lett. 2016, 18, 3194.
	Kumar, R.; Dwivedi, V.; Reddy, M.S. Adv. Synth. Catal. 2017, 359, 2847.
	Guo, Y.-J.; Lu, S.; Tian, L.-L.; Huang, E.-L.; Hao, X.-Q.; Zhu, X.; Shao, T.; Song, M.-P. J. Org. Chem. 2018, 83, 338.
	Zhang, J.; Liang, Z.; Wang, J.; Guo, Z.; Liu, C.; Xie, M. ACS Omega 2018, 3, 18002.
	Xie, F.; Lu, G.-P.; Xie, R.; Chen, Q.-H.; Jiang, H.-F.; Zhang, M. ACS Catal. 2019, 9, 2718.
[18]	Li, Y. ; Brand, J.P. ; Waser, J. Angew. Chem. , Int. Ed . 2013 , 52 , 6743.

Entry	Iodide salt	n(TolSO ₂Na)/mmol	Solvent	Yield ^b /%
1 ^c	KI	—	CH ₃OH	NR
2	KI	0.5	CH ₃OH	67
3	KI	0.6	CH ₃OH	80
4	KI	0.75	CH ₃OH	89
5	KI	0.85	CH ₃OH	88
6	NaI	0.75	CH ₃OH	85
7	ZnI ₂	0.75	CH ₃OH	68
8	NH ₄I	0.75	CH ₃OH	64
9	KI	0.75	C ₂ H ₅ OH	93
10	KI	0.75	CH ₃CN	87
11	KI	0.75	CH ₂Cl ₂	84
12	KI	0.75	p-Xylene	83
13	KI	0.75	DMF	Trace
14	KI	0.75	DMSO	Trace
15	KI	0.75	H ₂O	Trace
16 ^d	KI	0.75	C ₂H ₅OH	Trace

Entry	Iodide salt	n(TolSO ₂Na)/mmol	Solvent	Yield ^b /%
1 ^c	KI	—	CH ₃OH	NR
2	KI	0.5	CH ₃OH	67
3	KI	0.6	CH ₃OH	80
4	KI	0.75	CH ₃OH	89
5	KI	0.85	CH ₃OH	88
6	NaI	0.75	CH ₃OH	85
7	ZnI ₂	0.75	CH ₃OH	68
8	NH ₄I	0.75	CH ₃OH	64
9	KI	0.75	C ₂ H ₅ OH	93
10	KI	0.75	CH ₃CN	87
11	KI	0.75	CH ₂Cl ₂	84
12	KI	0.75	p-Xylene	83
13	KI	0.75	DMF	Trace
14	KI	0.75	DMSO	Trace
15	KI	0.75	H ₂O	Trace
16 ^d	KI	0.75	C ₂H ₅OH	Trace

对甲苯亚磺酸钠/KI介导端炔的需氧氧化碘代反应合成1-碘代炔和1,3-二炔

Sodiump-Toluenesulfinate/KI-Mediated Aerobic Oxidative Iodination of Terminal Alkynes for Synthesis of 1-Iodoalkynes and 1,3-Diynes

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