Rh(III)-Catalyzed Efficient Synthesis of Isocoumarins from Cyclohexanediones

doi:10.6023/cjoc202106017

Chinese Journal of Organic Chemistry ›› 2021, Vol. 41 ›› Issue (11): 4476-4483.DOI: 10.6023/cjoc202106017 Previous Articles Next Articles

ARTICLES

三价铑催化通过环己二酮高效构建异香豆素类化合物

戴雨倩, 李兴伟, 刘丙贤^*()

河南师范大学化学化工学院国家药监局创新药物研究与评价重点实验室河南省精细化工绿色生产协同创新中心河南新乡 453007

收稿日期:2021-06-08 修回日期:2021-07-13 发布日期:2021-07-26
通讯作者: 刘丙贤
基金资助:
国家自然科学基金(21801066); 国家自然科学基金(21525208); 国家自然科学基金(U1804283); 国家自然科学基金(21801067); 国家博士后科学基金(2020M682307); 国家博士后科学基金(2021T140183)

Rh(III)-Catalyzed Efficient Synthesis of Isocoumarins from Cyclohexanediones

Yuqian Dai, Xingwei Li, Bingxian Liu()

NMPA Key Laboratory for Research and Evaluation of Innovative Drug, Collaborative Innovation Center of Henan Province for Green Manufacturing of Fine Chemicals, School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, Henan 453007

Received:2021-06-08 Revised:2021-07-13 Published:2021-07-26
Contact: Bingxian Liu
Supported by:
National Natural Science Foundation of China(21801066); National Natural Science Foundation of China(21525208); National Natural Science Foundation of China(U1804283); National Natural Science Foundation of China(21801067); China Postdoctoral Science Foundation(2020M682307); China Postdoctoral Science Foundation(2021T140183)

1. .pdf(1859KB)

Abstract

Isocoumarin skeleton is a kind of important motif of natural product and bio-active molecular. The synthesis of simple and efficient construction of isocoumarin is of great significance. This work realized the one-pot synthesis of cyclohexanone-isocoumarins by rohdium catalyzed aryl C—H activation and followed annulation with in-situ generated iodonium ylides of cyclohexanones. Divers directing groups can be tolerated under the system leading to the desired products, among which sulfoxonium ylides and benzoic acids exhibited good reaction efficiency. Control experiments, deuterium labeling experiments and isolation of the possible intermediate revealed that the in-situ generated iodonium ylides were necessary for the reaction system.

Key words: isocoumarins, iodonium ylides, C—H activation, Rh-catalysis

Cite this article

Yuqian Dai, Xingwei Li, Bingxian Liu. Rh(III)-Catalyzed Efficient Synthesis of Isocoumarins from Cyclohexanediones[J]. Chinese Journal of Organic Chemistry, 2021, 41(11): 4476-4483.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 9

Figure 1. Isocoumarin-related natural products and synthetic intermediate

Scheme 1. Methods for the construction of cyclohexanone-isocoumarins

Entry	Base (2.5 equiv.)	Solvent (1 mL)	Yield/%
1	—	HFIP	65%
2^b	—	HFIP	n.d.
3	—	acetone	n.d.
4	—	THF	n.d.
5	—	DCE	n.d.
6	—	EA	n.d.
7	—	TFE	n.d.
8	—	EtOH	n.d.
9	KOH	HFIP	54%
10	NaOAc	HFIP	32%
11	K₂CO₃	HFIP	28%
12	LiOH	HFIP	10%
13	NaOMe	HFIP	28%
14	LiO^tBu	HFIP	26%
15	K₃PO₄	HFIP	96%
16^c	K₃PO₄	HFIP	n.d.
17

Table 1. Optimization of the standard reaction conditions

Table 2. Application scopes of sulfoxonium ylides and benzoic acids

Table 3. Application scope of cyclohexanediones

Scheme 2. Control experiments of the iodonium ylide intermediate

Scheme 3. Synthesis and reactions of the intermediate

Scheme 4. Deuterium labeling experiments

Scheme 5. Possible catalytic cycle

References 16

[1]	(a) Schwartz, B. D.; Banwell, M. G.; Cade, I. A. Tetrahedron Lett. 2011, 52, 4526. doi: 10.1016/j.tetlet.2011.06.050 pmid: 27597418
	(b) Yang, S.; Banwell, M. G.; Willis, A. C.; Ward, J. S. Aust. J. Chem. 2015, 68, 241. doi: 10.1071/CH14520 pmid: 27597418
	(c) Ibn-Ahmed, S.; Khaldi, M.; Chrétien, F.; Chapleur, Y. J. Org. Chem. 2004, 69, 6722. pmid: 27597418
	(d) Ramanan, M.; Sinha, S.; Sudarshan, K.; Aidhen, I. S.; Doble, M. Eur. J. Med. Chem. 2016, 124, 428. doi: S0223-5234(16)30724-3 pmid: 27597418
	(e) Xu, X.; Li, J.; Zhang, K.; Wei, S.; Lin, R.; Polyak, S. W.; Yang, N.; Song, F. Mar. Drugs 2021, 19, 313. doi: 10.3390/md19060313 pmid: 27597418
	(f) Zhao, J.-Q.; Wang, Y.-M.; Wang, S.; Dang, J.; Shi, Y.-P.; Mei, L.-J.; Tao, Y.-D. Nat. Prod. Res. 2016, 30, 1746. doi: 10.1080/14786419.2015.1137574 pmid: 27597418
[2]	Akagi, Y.; Yamada, S.; Etomi, N.; Kumamoto, T.; Nakanishi, W.; Ishikawa, T. Tetrahedron Lett. 2010, 51, 1338. doi: 10.1016/j.tetlet.2010.01.014
[3]	(a) Ashraf, Z. Chem. Heterocycl. Compd. 2016, 52, 149. doi: 10.1007/s10593-016-1849-z
	(b) Saikia, P.; Gogoi, S. Adv. Synth. Catal. 2018, 360, 2063. doi: 10.1002/adsc.v360.11
[4]	(a) Jiang, Y.; Li, P.; Zhao, J.; Liu, B.; Li, X. Org. Lett. 2020, 22, 7475. doi: 10.1021/acs.orglett.0c02618
	(b) Dong, Z.; Li, P.; Li, X.; Liu, B. Chin. J. Chem. 2021, 39, 3489.
[5]	(a) Plunkett, S.; DeRatt, L. G.; Kuduk, S. D.; Balsells, J. Org. Lett. 2020, 22, 7662. doi: 10.1021/acs.orglett.0c02851 pmid: 32969657
	(b) Bryson, T. A.; Stewart, J. J.; Gibson, J. M.; Thomas, P. S.; Berch, J. K. Green Chem. 2003, 5, 174. doi: 10.1039/b211966h pmid: 32969657
	(c) Fan, X.; He, Y.; Cui, L.; Guo, S.; Wang, J.; Zhang, X. Eur. J. Org. Chem. 2012, 2012, 673. pmid: 32969657
	(d) Dong, F.; Liu, J.-Q.; Wang, X.-S. J. Heterocycl. Chem. 2019, 56, 2822. doi: 10.1002/jhet.v56.10 pmid: 32969657
[6]	(a) He, X.; Han, G.; Zuo, Y.; Shang, Y. Tetrahedron 2018, 74, 7082. doi: 10.1016/j.tet.2018.10.045
	(b) Yang, C.; He, X.; Zhang, L.; Han, G.; Zuo, Y.; Shang, Y. J. Org. Chem. 2017, 82, 2081. doi: 10.1021/acs.joc.6b02906
	(c) Li, Y.; Wang, Q.; Yang, X.; Xie, F.; Li, X. Org. Lett. 2017, 19, 3410. doi: 10.1021/acs.orglett.7b01365
	(d) Li, X. G.; Sun, M.; Liu, K.; Jin, Q.; Liu, P. N. Chem. Commun. 2015, 51, 2380. doi: 10.1039/C4CC09314C
	(e) Zuo, Y.; He, X.; Ning, Y.; Zhang, L.; Wu, Y.; Shang, Y. New J. Chem. 2018, 42, 1673 doi: 10.1039/C7NJ03799F
	(f) Gao, C.; Li, B.; Geng, X.; Zhou, Q.; Zhang, X.; Fan, X. Green Chem. 2019, 21, 5113. doi: 10.1039/C9GC02001B
[7]	(a) Mayakrishnan, S.; Tamizmani, M.; Maheswari, N. U. Chem. Commun. 2020, 56, 15462. doi: 10.1039/D0CC06038K
	(b) Jia, M.; Ma, S. Angew. Chem., Int. Ed. 2016, 55, 9134. doi: 10.1002/anie.v55.32
[8]	Hong, C.; Jiang, X.; Yu, S.; Liu, Z.; Zhang, Y. Chin. J. Org. Chem. 2021, 41, 888. (in Chinese) doi: 10.6023/cjoc202007037
	(洪超, 蒋希程, 于书玲, 刘占祥, 张玉红, 有机化学, 2021, 41, 888.) doi: 10.6023/cjoc202007037
[9]	(a) Chen, Z.; Wang, B.; Zhang, J.; Yu, W.; Liu, Z.; Zhang, Y. Org. Chem. Front. 2015, 2, 1107. doi: 10.1039/C5QO00004A pmid: 30033454
	(b) Sambiagio, C.; Schonbauer, D.; Blieck, R.; Dao-Huy, T.; Pototschnig, G.; Schaaf, P.; Wiesinger, T.; Zia, M. F.; Wencel-Delord, J.; Besset, T.; Maes, B. U. W.; Schnurch, M. Chem. Soc. Rev. 2018, 47, 6603. doi: 10.1039/c8cs00201k pmid: 30033454
[10]	(a) Drapeau, M. P.; Gooßen, L. J. Chem.-Eur. J. 2016, 22, 18654. doi: 10.1002/chem.v22.52
	(b) Uttry, A.; Gemmeren, M. Synthesis 2020, 52, 479. doi: 10.1055/s-0039-1690720
[11]	Benzoyl chloride could react with the solvent to form the corresponding ester. Thus C―H activation can be realized by direction of ester group. The reaction can also occur by the use of pre-syn- thesized hexafluoroisopropyl benzoate, giving the product with 26% yield.
[12]	(a) Park, S. H.; Kim, J. Y..; Chang, S. Org. Lett. 2011, 13, 2372. doi: 10.1021/ol200600p
	(b) Yang, Y.; Lin, Y.; Rao, Y. Org. Lett. 2012, 14, 2874. doi: 10.1021/ol301104n
	(c) Wang, S.-M.; Moku, B.; Leng, J.; Qin, H.-L. Eur. J. Org. Chem. 2018, 4407.
[13]	Luo, J.; Fu, Q. Adv. Syn. Catal. 2021, 363, 3868. doi: 10.1002/adsc.v363.16
[14]	Tóth, B. L.; Monory, A.; Egyed, O.; Domján, A.; Bényei, A.; Szathury, B.; Novák, Z.; Stirling, A. Chem. Sci. 2021, 12, 5152. doi: 10.1039/D1SC00642H
[15]	Sharma, K.; Neog, K.; Gogoi, P. Org. Lett. 2020, 22, 73. doi: 10.1021/acs.orglett.9b03932 pmid: 31815487
[16]	Jambu, S.; Jeganmohan, M. Org. Lett. 2020, 22, 5057. doi: 10.1021/acs.orglett.0c01636

三价铑催化通过环己二酮高效构建异香豆素类化合物

Rh(III)-Catalyzed Efficient Synthesis of Isocoumarins from Cyclohexanediones

RichHTML

PDF

Supporting Info.

Knowledge

Abstract

Cite this article

share this article

Fig. & Tab. 9

References 16

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	Jiling Yi, Kangqi Shi, Binglin Wu, Wanshan Li, Guangying Chen. Study on Secondary Metabolites of Marine-Derived Fungus Eutypella sp. F0219 [J]. Chinese Journal of Organic Chemistry, 2023, 43(1): 295-298.
[2]	Fei Chen, Sheng Tao, Ning Liu, Bin Dai. CNN-Type Binuclear Cu(I) Complexes Catalyzed Direct Carboxylation via the Fixation of CO₂ at Room Temperature [J]. Chinese Journal of Organic Chemistry, 2022, 42(8): 2471-2480.
[3]	Cheng Gong, Jian Tang, Fei Xu, Pengjie Li, Zetian Wang, Yumin Zhang, Guoxian Yu, Liang Wang. Recent Advances in Transition-Metal-Catalyzed C—H Activation of Pyridone/Isoquinolones [J]. Chinese Journal of Organic Chemistry, 2022, 42(7): 1925-1949.
[4]	Chengyao Kimmy Cao, Yaru Niu, Yunchen Jiang, Hongmei Qu, Chao Chen. Pd-Catalyzed Chlorodifluoroethylation Reaction of C—H Bond of Acetanilides with Chlorodifluoroethyl Iodonium Reagents [J]. Chinese Journal of Organic Chemistry, 2022, 42(7): 2098-2105.
[5]	Chaoyu Wang, Shuda Dong, Tianyang Zhu, Yuqin Liu, Zihan Wu, Ruokun Feng. Cobalt-Catalyzed Decarbonylative C(8)-Acyloxylation of 1-Naphthalamine Derivatives with α-Oxocarboxylic Acids [J]. Chinese Journal of Organic Chemistry, 2022, 42(6): 1799-1810.
[6]	Xinyao Wang, Qingqing Zhang, Shuyang Liu, Min Li, Haifang Li, Chunying Duan, Yunhe Jin. Visible Light-Induced Metal-Free Benzylation of Quinones via Cross Dehydrogenation Coupling Reaction [J]. Chinese Journal of Organic Chemistry, 2022, 42(5): 1443-1452.
[7]	Yudong Li, Ying Li, Ya'nan Dong, Chungu Xia, Yuehui Li. Manganese-Catalyzed Allylation of Quinazolinones with 4-Vinyl-1,3-dioxolan-2-one via C—H Activation [J]. Chinese Journal of Organic Chemistry, 2022, 42(3): 847-853.
[8]	Jiazhuang Wang, Liguo Teng, Shaoqi Xiong, Tiebo Xiao, Yubo Jiang. Rh-Catalyzed gem-Difluoroallylation of N-Tosylhydrazones [J]. Chinese Journal of Organic Chemistry, 2022, 42(11): 3658-3667.
[9]	Lingjie Fan, Tao Zhou, Xu Yang, Mengxue Jiang, Xinquan Hu, Bingfeng Shi. Pd(II)-Catalyzed Enantioselective C—H Olefination of 2-(Arylsulfinyl)pyridines through Kinetic Resolution [J]. Chinese Journal of Organic Chemistry, 2022, 42(10): 3405-3418.
[10]	Huanhuan Luo, Na Pei, Jing Zhang. Advances in Nitrogen-Directed Aromatic Compound ortho-C—H Bond Borylation Catalyzed by Transition Metals [J]. Chinese Journal of Organic Chemistry, 2021, 41(8): 2990-3001.
[11]	Man Xu, Yuanzhi Xia. Mechanistic Understanding of Rh(III)-Catalyzed Redox-Neutral C—H Activation/Annulation Reactions of N-Phenoxyacetamides and Methyleneoxetanones [J]. Chinese Journal of Organic Chemistry, 2021, 41(8): 3272-3278.
[12]	Xiaoliang Zou, Senmiao Xu. Recent Progress in Iridium-Catalyzed Remote Regioselective C—H Borylation of (Hetero)Arenes [J]. Chinese Journal of Organic Chemistry, 2021, 41(7): 2610-2620.
[13]	Mingyang Sun, Kun Xu, Bingbing Guo, Chengchu Zeng. Copper-Catalyzed Vicinal C(sp²)—H Selenylation of Benzoic Acid Derivatives Using Air as Oxidant [J]. Chinese Journal of Organic Chemistry, 2021, 41(6): 2302-2309.
[14]	Ya-Lan Feng, Bing-Feng Shi. Recent Advances in Base Metal (Copper, Cobalt and Nickel)-Catalyzed Directed C—H Amination [J]. Chinese Journal of Organic Chemistry, 2021, 41(10): 3753-3770.
[15]	Fang Zhixing, Liu Juyan, Qiao Yanhong. Bromodimethylsulfonium Bromide Catalyzed Synthesis of Pyrazole-Fused Isocoumarins [J]. Chin. J. Org. Chem., 2018, 38(8): 1985-1992.