Visible-Light-Induced Dearomatizing Spirocyclization of Alkenes Toward Perfluorinated Azaspirocyclic Cyclohexadienones

doi:10.11944/j.issn.1000-0518.2018.02.170099

Chinese Journal of Applied Chemistry ›› 2018, Vol. 35 ›› Issue (2): 181-188.DOI: 10.11944/j.issn.1000-0518.2018.02.170099

• Full Papers • Previous Articles Next Articles

Visible-Light-Induced Dearomatizing Spirocyclization of Alkenes Toward Perfluorinated Azaspirocyclic Cyclohexadienones

YUAN Li,LI Zengzeng,JIANG Shengming,ZHU Yong,LEI Qian,XIA Lülu,LI Lan,YU Jian,ZHANG Juan,TANG Shi()

College of Chemistry and Chemical Engineering,Engineering Laboratory for Analyse and Drugs Development of Ethnomedicine in Wuling Mountains,Jishou University,Jishou,Hu'nan 416000,China

Received:2017-04-01 Accepted:2017-05-18 Published:2018-02-01 Online:2018-01-29
Contact: TANG Shi
Supported by:
Supported by the National Natural Science Foundation of China(No.21462017, No.21662013), the Research Innovation Program for Graduates in Hu'nan province(No.16A171)

Abstract

Abstract:

A visible-light-induced dearomation cyclilation of N-benzylmethacrylamides with nonafluorinated alkyl bromides or iodides toward nonafluorinated azaspirocyclic cyclo-hexadienones was developed. Under the irradiation of blue light-emitting diode(LED) light, using fac-Ir(ppy)₃(fac=facial, ppy=2-phenylpyridyl) as the photocatalyst, N-benzylmethacrylamides and nonafluorinated alkyl bromides or iodides underwent cascade dearomation/cyclilation under optimal conditions, leading to a series of perfluorinating azaspirocyclic cyclohexadienones in 61%85% yield, as well as introducing a series of perfluorinated moieties including CF₃, C₃F₇, C₄F₉, C₆F₁₃, C₈F₁₇, CH₂CF₂, CF₂CO₂Et(Et:Ethyl). Given the broad substrate scope, mild reaction conditions and green catalytic systems, this protocol provides a green, effective and quick approach to pharmaceutically important cyclohexadienones.

Key words: perfluorinated, dearomative cyclilation, visible-light-induced, azaspirocyclic cyclohexadienones

YUAN Li, LI Zengzeng, JIANG Shengming, ZHU Yong, LEI Qian, XIA Lülu, LI Lan, YU Jian, ZHANG Juan, TANG Shi. Visible-Light-Induced Dearomatizing Spirocyclization of Alkenes Toward Perfluorinated Azaspirocyclic Cyclohexadienones[J]. Chinese Journal of Applied Chemistry, 2018, 35(2): 181-188.

References

[1]	Rousseaux S,García-Fortanet J,Del M A,et al.Palladium(0)-Catalyzed Arylative Dearomatization of Phenols[J]. J Am Chem Soc,2011,133(24):9282-9285.
[2]	Kazmierski W M,Furfine E,Spaltenstein A,et al.Novel Spirocyclic Pyrrolidones as P2/P1 Mimetics in Potent Inhibitors of HIV-1 Protease[J]. Bioorg Med Chem Lett,2002,12(23):3431-3433.
[3]	Badger A M,Newman-Tarr T M,Satterfield J L,et al. Selective Immunomodulatory Activity of SK&F 106615, a Macrophage-Targeting Antiarthritic Compound, on Antibody and Cellular Responses in Rats and Mice[J]. Immunopharmacology,1997,37(1):53-61.
[4]	Ortiz F L,Iglesias M J,Fernández I,et al.Nucleophilic Dearomatizing(DNAr) Reactions of Aromatic C,H-Systems. A Mature Paradigm in Organic Synthesis[J]. Chem Rev,2007,107(5):1580-1897.
[5]	Hagmann W K.The Many Roles for Fluorine in Medicinal Chemistry[J]. J Med Chem,2008,51(15):4359-4369.
[6]	Gu Z,Zhang H,Xu P,et al.Visible-Light-Induced Radical Tandem Aryldifluoroacetylation of Cinnamamides:Access to Difluoroacetylated Quinolone-2-ones and 1-Azaspiro[4.5]decanes[J]. Adv Synth Catal,2015,357(14):3057-3063.
[7]	Han G F,Liu Y X,Wang Q M,et al.Copper-Catalyzed Intramolecular Trifluoromethylation of N-Benzylacrylamides Coupled with Dearomatization:Access to CF3-Containing 2-Azaspiro[4.5]decanes[J]. Org Lett,2014,16(12):3188-3191.
[8]	Han G F,Liu Y X,Wang Q M,et al.Copper-Mediated α-Trifluoromethylation of N-Phenylcinnamamides Coupled with Dearomatization:Access to Trifluoromethylated 1-Azaspiro[4.5]decanes[J]. Org Lett,2014,16(22):5914-5917.
[9]	Zhang Z X,Tang X J,Dolbier Jr R,et al.Photoredox-Catalyzed Intramolecular Difluoromethylation of N-Benzylacrylamides Coupled with a Dearomatizing Spirocyclization: Access to CF2H-Containing 2-Azaspiro[4.5]deca-6,9-diene-3,8-diones[J]. Org Lett,2016,18(5):1048-1051.
[10]	Zuo Z,Almema D T,Terrett J A,et al.Merging Photoredox with Nickel Catalysis:Coupling of α-Carboxyl sp3-Carbons with Aryl Halides[J]. Science,2014,345(6195):437-440.
[11]	Hu B,Li Y,Dong W H,et al.Visible Light-induced Intramolecular Dearomative Cyclization of α-Bromo-N-benzyl-alkylamides:Efficient Construction of 2-Azaspiro[4.5]Decanes[J]. Chem Commun,2016,52(18):3709-3712.
[12]	Tang S,Deng Y L,Li J,et al.Perfluorinated Isoquinolinediones Through Visible-Light-Induced Cyclization of Alkenes[J]. J Org Chem,2015,80(24):12599-12605.

Visible-Light-Induced Dearomatizing Spirocyclization of Alkenes Toward Perfluorinated Azaspirocyclic Cyclohexadienones

RichHTML

PDF

Knowledge

Cited

Abstract

Cite this article

share this article

References

Related Articles 6

Recommended Articles

Metrics

Comments

[1]	Shi-Peng JIANG, Yu-Xi ZHOU, Pei-Ran MENG, Yan-Xuan XIE, Zhi-Yi SONG, Huan-Ying ZHAO, Yue SUN. Preparation and Properties of Ultramicro Imprinting Sensor for Human Serum Albumin via Metal-free Visible-light-induced Atom Transfer Radical Polymerization [J]. Chinese Journal of Applied Chemistry, 2023, 40(2): 299-308.
[2]	LI Jie, LIU Yilin, DENG Youlin, WANG Wenxin, WANG Shuowen, LI Zengzeng, TANG Shi. Visible-Light-Induced Cyclization of Alkenes to Form Difluoroacetating Isoquinolinedione [J]. Chinese Journal of Applied Chemistry, 2016, 33(6): 677-684.
[3]	DENG Youlin, TANG Shi, ZHANG Qian, WANG Qiong, PENG Menglu, YU Limin. Visible-light-induced Cascade Addition Cyclization of Alkenes Toward Perfluoroalkylated Isoquinolinediones [J]. Chinese Journal of Applied Chemistry, 2016, 33(6): 685-692.
[4]	TANG Shi, LI Zhihao, DENG Youlin, GAN Yabing, YUAN Shiliang, ZHOU Xiangqi. Metal-free Cyclization of Alkenes Toward Perfluorinated Oxindoles [J]. Chinese Journal of Applied Chemistry, 2015, 32(11): 1246-1252.
[5]	ZHANG Daihui1,2*, LU Lijun1, ZHANG Xun1, MU Jun1, ZHOU Xiao1, HU Tingting1, HAN Dachuan1. Simultaneous Determination of Ten Kinds of Perfluorinated Compounds in Lubricant Samples by High-performance Liquid Chromatography-Tandem Mass Spectrometry [J]. Chinese Journal of Applied Chemistry, 2012, 29(10): 1163-1170.
[6]	Zu Yanbing, Cha Chuansin. Improvement of Hydtophilicity of Nafion Membrane Surface by Modification with Perfluorinated Sutfactants [J]. Chinese Journal of Applied Chemistry, 1995, 0(2): 33-36.