可见光催化的1,6-烯炔参与的Kharasch加成反应

doi:10.6023/cjoc202106014

有机化学 ›› 2021, Vol. 41 ›› Issue (12): 4815-4824.DOI: 10.6023/cjoc202106014 上一篇下一篇

所属专题：有机光催化虚拟合辑；绿色合成化学专辑；热点论文虚拟合集

研究论文

可见光催化的1,6-烯炔参与的Kharasch加成反应

耿芳洲^a^,^b, 王世超^a, 宋克贤^a, 郝文娟^a^,^b^,^*(), 姜波^a^,^b^,^*()

a 江苏师范大学化学与材料科学学院江苏徐州 221116
b 江苏师范大学敬文书院江苏徐州 221116

收稿日期:2021-06-07 修回日期:2021-07-14 发布日期:2021-07-19
通讯作者: 郝文娟, 姜波
作者简介:
† 共同第一作者
基金资助:
国家自然科学基金(21971090); 江苏省品牌专业基金和国家级大学生创新创业训练计划(202010320060Z)

Visible-Light-Driven Photocatalytic Kharasch-Type Addition of 1,6-Enynes

Fangzhou Geng^a^,^b, Shichao Wang^a, Kexian Song^a, Wenjuan Hao^a^,^b(), Bo Jiang^a^,^b()

a School of Chemistry & Materials Science, Jiangsu Normal University, Xuzhou, Jiangsu 221116
b C.W. Chu College, Jiangsu Normal University, Xuzhou, Jiangsu 221116

Received:2021-06-07 Revised:2021-07-14 Published:2021-07-19
Contact: Wenjuan Hao, Bo Jiang
About author:
† These authors contributed equally to this work.
Supported by:
National Natural Science Foundation of China(21971090); Top-notch Academic Programs Project of Jiangsu Higher Education Institutions and National College Studentʼs Innovation and Entrepreneurship Training Program(202010320060Z)

文章分享

1. 214815S.pdf(3870KB)

摘要/Abstract

报道了一类新颖的可见光催化的1,6-烯炔参与的Kharasch加成反应. 该反应利用三氯溴甲烷和四溴化碳在光催化还原下能产生三卤代甲基自由基的特性, 实现其在fac-Ir(ppy)₃与可见光作用下与1,6-烯炔发生Kharasch加成反应, 区域选择性地合成了具有环外双键以及季碳的1-茚酮衍生物, 产率中等至良好. 基于实验结果及文献报道, 提出了合理的反应机理, 涉及三卤代甲基自由基的原位形成、自由基引发的加成环化以及自由基交叉偶联等. 此外, 该反应具有底物普适性广、高官能团兼容性、100%原子利用率、条件温和、操作简便等优点, 从而为具有潜在应用价值的1-茚酮骨架的构建提供了一种绿色、温和且高效的合成策略, 符合绿色化学理念.

关键词: Kharasch加成, 可见光催化反应, 1,6-烯炔衍生物, 1-茚酮衍生物

A new visible-light-driven photocatalytic Kharasch-type addition of 1,6-enynes was reported. By using the characteristics of the in-situ-generation of trihalomethyl radicals from photocatalytic reduction of trichloromethane bromide and carbon tetrabromide, fac-Ir(ppy)₃-catalyzed Kharasch-type addition of 1,6-enynes of these polyhalogenated hydrocarbon substrates at room temperature was conducted under visible-light irradiation, regioselectively affording 1-indanone derivatives with an exocyclic double bond and a quaternary carbon in moderate to good yields. Based on the experimental results and literature reports, a reasonable reaction mechanism was proposed, which involved the in-situ-generation of trihalomethyl radicals, radical-induced addition-cyclization and radical cross coupling. In addition, this protocol featured wide substrate scope, high functional group compatibility, 100% atomic utilization, and mild conditions as well as simple operation. It provides a green, mild, and efficient synthetic strategy for the construction of 1-indanone skeleton with potential application, which is consistent with the concept of green chemistry.

Key words: Kharasch-type addition, photocatalysis, 1,6-enynes, 1-indanones

引用此文

耿芳洲, 王世超, 宋克贤, 郝文娟, 姜波. 可见光催化的1,6-烯炔参与的Kharasch加成反应[J]. 有机化学, 2021, 41(12): 4815-4824.

Fangzhou Geng, Shichao Wang, Kexian Song, Wenjuan Hao, Bo Jiang. Visible-Light-Driven Photocatalytic Kharasch-Type Addition of 1,6-Enynes[J]. Chinese Journal of Organic Chemistry, 2021, 41(12): 4815-4824.

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

分享此文

图/表 7

图1. 代表性的含1-茚酮骨架的天然产物

Figure 1. Representative 1-indanone-containing natural products

图式1. 可见光催化的Kharasch加成反应

Scheme 1. Visible-light-driven photocatalytic Kharasch-type addition

Entry	Variation of the established conditions	Yield/%
1	None	85
2	4.0 Equiv. of BrCCl₃	80
3	3.0 Equiv. of BrCCl₃	41
4	AgSCF₃ instead of AgOAc	73
5	10 mol% of AgOAc	Trace
6	50 mol% of AgOAc	36
7	Ru(bpy)₃Cl₂•6H₂O instead of fac-Ir(ppy)₃	80
8	Eosin Y instead of fac-Ir(ppy)₃	67
9	Without fac-Ir(ppy)₃	0
10	No light	0
11	CH₃CN as solvent	72
12	THF as solvent	Trace
13	K₂CO₃ instead of NaOAc	64
14	CsCO₃ instead of NaOAc	68

表1. 化合物3aa反应条件的优化a

Table 1. Optimization of reaction conditions for the synthesis of 3aa

图式2. 1-茚酮衍生物3的合成

Scheme 2. Synthesis of 1-indanones 3

图式3. 控制反应

Scheme 3. Controlled Experiments

图2. 1-茚酮衍生物3ha的晶体结构图

Figure 2. X-ray structure of 1-indanone 3ha

图式4. 生成化合物3的可能机理

Scheme 4. Proposed mechanism for the synthesis of product 3

参考文献 17

[1]	(a) Nagle, D. G.; Zhou, Y. D.; Park, P. U.; Paul, V. J.; Rajbhandari, I.; Duncan, C. J. G.; Pasco, D. S. J. Nat. Prod. 2000, 63, 1431. pmid: 7490731
	(b) Ito, T.; anaka, T.; Iinuma, T. M.; Nakaya, K.; Takahashi, Y.; Sawa, R.; Murata, J.; Darnaedi, D. J. Nat. Prod. 2004, 67, 932. doi: 10.1021/np030236r pmid: 7490731
	(c) Dai, J. R.; Hallock, Y. F.; Cardellina, J. H.; Boyd, M. R. J. Nat. Prod. 1998, 61, 351. pmid: 7490731
	(d) DeSolms, S. J.; Woltersdorf, O. W.; Cragoe, E. J.; Watson, L. S.; Fanelli, G. M. J. Med. Chem. 1978, 21, 437. doi: 10.1021/jm00203a006 pmid: 7490731
	(e) Sugimoto, H.; Iimura, Y.; Yamanishi, Y.; Yamatsu, K. J. Med. Chem. 1995, 38, 4821. pmid: 7490731
[2]	(a) Anstead, G. M.; Wilson, S. R.; Katzenellenbogen, J. A. J. Med. Chem. 1989, 32, 2163. pmid: 15876535
	(b) McDevitt, R. E.; Malamas, M. S.; Manas, E. S.; Unwalla, R. J.; Xu, Z. B.; Miller, C. P.; Harris, H. A. Bioorg. Med. Chem. Lett. 2005, 15, 3137. pmid: 15876535
	(c) Park, C. H.; Siomboing, X.; Yous, S.; Gressier, B; Luyckx, M.; Chavatte, P. Eur. J. Med. Chem. 2002, 37, 461-468. doi: 10.1016/S0223-5234(02)01373-9 pmid: 15876535
[3]	(a) Ahn, J. H.; Shin, M. S.; Jung, S. H.; Kang, S. K.; Kim, K. R.; Dal Rhee, S.; Jung, W. H.; Yang, S. D.; Kim, S. J.; Woo, J. R. J. Med. Chem. 2006, 49, 4781. doi: 10.1021/jm060389m pmid: 22536944
	(b) Kiselev, E.; DeGuire, S.; Morrell, A.; Agama, K.; Dexheimer, T. S.; Pommier, Y.; Cushman, M. J. Med. Chem. 2011, 54, 6106. doi: 10.1021/jm200719v pmid: 22536944
	(c) Nguyen, T. X.; Morrell, A.; Conda-Sheridan, M.; Marchand, C.; Agama, K.; Bermingam, A.; Stephen, A. G; Chergui, A.; Naumova, A.; Fisher, R.; O’Keefe, B. R.; Pommier, Y.; Cushman, M. J. Med. Chem. 2012, 55, 4457. doi: 10.1021/jm300335n pmid: 22536944
	(d) Gamo, F. J.; Sanz, L. M.; Vidal, J.; de, C. C.; Alvarez, E.; Lavandera, J. L.; Vanderwall, D. E. Green, D. V. S.; Kumar, V.; Hasan, S.; Brown, J. R.; Peishoff, C. E.; Cardon, L. R.; Garcia-Bustos, J. F. Nature 2010, 465, 305. doi: 10.1038/nature09107 pmid: 22536944
[4]	(a) Liu, W.; Buck, M.; Chen, N.; Shang, M.; Taylor, N. J.; Asoud, J.; Wu, X.; Hasinoff, B. B.; Dmitrienko, G. I. Org. Lett. 2007, 9, 2915. doi: 10.1021/ol0712374 pmid: 19902905
	(b) Jeffrey, J. L.; Sarpong, R.; Org. Lett. 2009, 11, 5450. doi: 10.1021/ol902141z pmid: 19902905
[5]	(a) Cappelli, A.; Pericot Mohr, G. L.; Giuliani, G.; Galeazzi, S.; Anzini, M.; Mennuni, L.; Ferrari, F.; Makovec, F.; Kleinrath, E. M.; Langer, T.; Valoti, M.; Giorgi, G.; Vomero, S. J. Med. Chem. 2006, 49, 6451. pmid: 17064065
	(b) Tseng, C. H.; Tzeng, C. C.; Yang, C. L.; Lu, P. J.; Chen, H. L.; Li, H. Y.; Chuang, Y. C.; Yang, C. N.; Chen, Y. L. J. Med. Chem. 2010, 53, 6169. pmid: 17064065
[6]	(a) Koelsch, C. F. J. Am. Chem. Soc. 1932, 54, 2487. doi: 10.1021/ja01345a046
	(b) Frank, R. L.; Eklund, H. J.; Richter, W.; Vanneman, C. R.; Wennerberg, A. N. J. Am. Chem. Soc. 1944, 66, 1. doi: 10.1021/ja01229a001
[7]	(a) Bergmann, E. D. J. Org. Chem. 1956, 21, 461. doi: 10.1021/jo01110a023
	(b) Manning, C.; McClory, M. R.; McCullough, J. J. J. Org. Chem. 1981, 46, 919. doi: 10.1021/jo00318a018
	(c) Dong, D.-Q.; Chen, W.-J.; Chen, D.-M.; Li, L. X..; Li, G. H.; Wang, Z. L.; Deng, Q.; Long, S. Chin. J. Org. Chem. 2019, 39, 3190. (in Chinese) doi: 10.6023/cjoc201904070
	( 董道青, 陈文静, 陈德茂, 李丽霞, 李光辉, 王祖利, 邓企, 龙姝, 有机化学, 2019, 39, 3190.) doi: 10.6023/cjoc201904070
[8]	(a) Chernyak, N.; Gorelsky, S. I.; Gevorgyan, V. Angew. Chem. Int. Ed. 2011, 50, 2342. doi: 10.1002/anie.201006751
	(b) Shintani, R.; Takatsu, K.; Hayashi, T. Angew. Chem. Int. Ed. 2007, 46, 3735. doi: 10.1002/(ISSN)1521-3773
	(c) He, G.; Wu, C.; Zhou, J.; Yang, Q.; Zhang, C.; Zhou, Y.; Zhang, H.; Liu, H. J. Org. Chem. 2018, 83, 13356. doi: 10.1021/acs.joc.8b02149
	(d) Song, L.; Tian, G.; Van der Eycken, E. V. Chem. Eur. J. 2019, 25, 7645. doi: 10.1002/chem.v25.32
	(e) Liu, Q.-S.; Lv, Y.-F.; Liu, R.-S.; Zhao, X.-H.; Wang, J.-W.; Wei, W. Chin. Chem. Lett. 2021, 32, 136. doi: 10.1016/j.cclet.2020.11.059
[9]	(a) Zhang, Y. L.; Sun, K.; Lv, Q. Y.; Chen, X. L.; Qu, L. B.; Yu, B. Chin. Chem. Lett. 2019, 30, 1361. doi: 10.1016/j.cclet.2019.03.034
	(b) Zhang, T.-S.; Hao, W.-J.; Wang, R.; Wang, S.-C.; Tu, S.-J.; Jiang, B. Green Chem. 2020, 22, 4259. doi: 10.1039/D0GC00771D
	(c) Shen, Z.-J.; Wu, Y.-N.; He, C.-L.; He, L.; Hao, W.-J.; Wang, A.-F.; Tu, S.-J.; Jiang, B. Chem. Commun. 2018, 54, 445. doi: 10.1039/C7CC08516H
	(d) Wu, Y.-N.; Zhang, T.-S.; Hao, W.-J.; Tu, S.-J.; Jiang, B. Asian J. Org. Chem. 2020, 9, 1040. doi: 10.1002/ajoc.v9.7
	(e) Wei, W.-T.; Li, Q.; Zhang, M.-Z.; He, W.-M. Chin. J. Catal. 2021, 42, 731. doi: 10.1016/S1872-2067(20)63702-0
	(f) Zhang, T.-S.; Hao, W.-J.; Cai, P.-J.; Li, G.; Tu, S.-J.; Jiang, B. Front. Chem. 2020, 8, 234. doi: 10.3389/fchem.2020.00234
[10]	Shi, H.-N.; Huang, M.-H.; Hao, W.-J.; Tu, X.-C.; Tu, S.-J.; Jiang, B. J. Org. Chem. 2019, 84, 16027. doi: 10.1021/acs.joc.9b02525 pmid: 31769289
[11]	Shen, Z.-J.; Wang, S.-C.; Hao, W.-J.; Yang, S.-Z.; Tu, S.-J.; Jiang, B. Adv. Synth. Catal. 2019, 361, 3837. doi: 10.1002/adsc.v361.16
[12]	(a) Prier, C. K.; Rankic, D. A.; MacMillan, D. W. C. Chem. Rev. 2013, 113, 5322. doi: 10.1021/cr300503r
	(b) Zhu, C.-F.; Zhang, J.; Zhu, Y.-L.; Hao, W.-J.; Tu, S.-J.; Wang, D.-C.; Jiang, B. Org. Chem. Front. 2021, 8, 1952. doi: 10.1039/D1QO00124H
	(c) Shi, J.; Wei, W. Chin. J. Org. Chem. 2020, 40, 2170. (in Chinese) doi: 10.6023/cjoc202000041
	( 时建伟, 魏伟, 有机化学, 2020, 40, 2170.) doi: 10.6023/cjoc202000041
	(d) Peng, S.; Lin, Y.-W.; He, W.-M. Chin. J. Org. Chem. 2020, 40, 541. (in Chinese) doi: 10.6023/cjoc202000006
	( 彭莎, 林英武, 何卫民, 有机化学, 2020, 40, 541.) doi: 10.6023/cjoc202000006
	(e) Yi, R.; He, W. Chin. J. Org. Chem. 2021, 41, 1267. (in Chinese) doi: 10.6023/cjoc202100022
	( 易荣楠, 何卫民, 有机化学, 2021, 41, 1267.) doi: 10.6023/cjoc202100022
	(f) Chen, J.-R.; Hu, X. Q.; Lu, L.-Q.; Xiao, W.-J. Chem. Soc. Rev. 2016, 45, 2044. doi: 10.1039/C5CS00655D
	(g) Xuan, J.; Zhang, Z. G.; Xiao, W.-J. Angew. Chem. Int. Ed. 2015, 54, 15632. doi: 10.1002/anie.v54.52
	(h) Huang, H. C.; Jia, K. F.; Chen, Y. ACS Catal. 2016, 6, 4983. doi: 10.1021/acscatal.6b01379
	(i) Mi, X.; Kong, Y. F.; Zhang, J. Y.; Pi, C.; Cui, X. L. Chin. Chem. Lett. 2019, 30, 2295. doi: 10.1016/j.cclet.2019.09.040
[13]	(a) Zhu, S.-S.; Zhou, J.-N.; Wu, Q.-L.; Hao, W.-J.; Tu, S.-J.; Jiang, B. Org. Chem. Front. 2020, 7, 2975. doi: 10.1039/D0QO00917B pmid: 31769294
	(b) Zhao, Q.; Hao, W.-J.; Shi, H.-N.; Xu, T.; Tu, S.-J.; Jiang, B. Org. Lett. 2019, 21, 9784. doi: 10.1021/acs.orglett.9b04018 pmid: 31769294
	(c) Gui, Q.-W.; Teng, F.; Li, Z.-C.; Xiong, Z.-Y.; Jin, X.-F.; Lin, Y.-W.; Cao, Z.; He, W.-M. Chin. Chem. Lett. 2021, 32, 1907. doi: 10.1016/j.cclet.2021.01.021 pmid: 31769294
	(d) Liu, K.-J.; Wang, Z.; Lu, L.-H.; Chen, J.-Y.; Zeng, F.; Lin, Y.-W.; Cao, Z.; Yu, X.; He, W.-M. Green Chem. 2021, 23, 496. doi: 10.1039/D0GC02663H pmid: 31769294
[14]	(a) Yu, X.-Y.; Chen, J.-R.; Xiao, W.-J. Chem. Rev. 2021, 121, 506. doi: 10.1021/acs.chemrev.0c00030
	(b) Yang, Z.; Stivanin, M. L.; Jurberg, I. D.; Koenigs, R. M. Chem. Soc. Rev. 2020, 49, 6833. doi: 10.1039/D0CS00224K
	(c) Chen, D. M.; Sun, Y. Y.; Dong, D. Q.; Han, Q. Q.; Wang, Z. L. Chin. J. Org. Chem. 2020, 40, 4267. (in Chinese) doi: 10.6023/cjoc202006025
	( 陈德茂, 孙媛媛, 董道青, 韩晴晴, 王祖利, 有机化学, 2020, 40, 4267.) doi: 10.6023/cjoc202006025
	(d) Meng, N.; Lv, Y. F.; Liu, Q. S.; Liu, R. S.; Zhao, X. H.; Wei, W. Chin. Chem. Lett. 2021, 32, 258. doi: 10.1016/j.cclet.2020.11.034
[15]	Wu, D.; Hao, W.-J.; Rao, Q.; Lu, Y.; Tu, S.-J.; Jiang, B. Chem. Commun. 2021, 57, 1911. doi: 10.1039/D0CC07880H
[16]	(a) Kharasch, M. S.; Jensen, E. V.; Urry, W. H. Science 1945, 102, 128. pmid: 17777366
	(b) Chen, B.; Fang, C.; Liu, P.; Ready, J. M. Angew. Chem., nt. Ed. 2017, 56, 8780. pmid: 17777366
	(c) Wang, L. L.; Zhang, M.; Zhang, Y. L.; Liu, Q. S.; Zhang, X. H.; Li, J. S.; Luo, Z. D.; Wei, W. Chin. Chem. Lett. 2020, 31, 67. doi: 10.1016/j.cclet.2019.05.041 pmid: 17777366
[17]	(a) Bacauanu, V.; Cardinal, S.; Yamauchi, M.; Kondo, M.; Fernandez, D. F.; Remy, R.; MacMillan, D. W. C. Angew. Chem., nt. Ed. 2018, 57, 12543.
	(b) Wang, S.-W.; Yu, J.; Zhou, Q.-Y.; Chen, S.-Y.; Xu, Z.-H. Tang, S. ACS Sustainable Chem. Eng. 2019, 7, 10154. doi: 10.1021/acssuschemeng.9b02178

可见光催化的1,6-烯炔参与的Kharasch加成反应

Visible-Light-Driven Photocatalytic Kharasch-Type Addition of 1,6-Enynes

RichHTML

PDF

补充材料

可视化

摘要/Abstract

引用此文

分享此文

图/表 7

参考文献 17

相关文章 2

编辑推荐

相关统计

本文评价

[1]	赵瑜, 段玉荣, 史时辉, 白育斌, 黄亮珠, 杨晓军, 张琰图, 冯彬, 张建波, 张秋禹. 可见光促进高价碘(III)试剂参与反应的研究进展[J]. 有机化学, 2023, 43(12): 4106-4140.
[2]	季晓霜, 付荣, 王树良, 郝文娟, 姜波. 可见光驱动酚/芳胺联-1,6-烯炔与全卤代甲烷的Kharasch反应[J]. 有机化学, 2022, 42(12): 4282-4291.