Advanced Search

Citation: Zhang Ling, Zhang Peizhi, Xue Jianfei, Sun Wangbin, Zou Jianping. Manganese Acetate-Mediated Phosphorylation of Indoles[J]. Acta Chimica Sinica, ;2016, 74(10): 811-818. doi: 10.6023/A16070351 shu

Manganese Acetate-Mediated Phosphorylation of Indoles

  • 1.

    Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry and Chemical Engineering, Soochow University, Suzhou, Jiangsu 215123

  • Corresponding author: Zou Jianping, 
  • Received Date: 19 July 2016

    Fund Project:

  • Mn(OAc)3-mediated selective radical phosphorylation of indoles with dialkylphosphites or diphenylphosphine oxide in moderate to good yields is described. The reaction proceeds under mild conditions in air, no need to add extra additives, through a radical process involving phosphorus-centered radical generated from dialkylphosphites or diphenylphosphine oxide mediated by Mn(OAc)3, selectively added to 3-position of 2-substituted indoles or 2-position of 3-substituted indoles to form carbon radical intermediate, followed by oxidation with Mn(OAc)3 and deprotonation to afford products 2- or 3-phosphonyl indoles. This protocol provides an efficient and general method for the preparation of 2- and 3-phosphoryl indoles. The detailed investigation revealed that 1) the yields of N-methyl indoles were higher than NH unprotected analogues; 2) 2-Phenyl or 2-methyl indoles were unsuitable for the reaction with dialkylphosphites, but were suitable for the reaction with diphenyl phosphine oxide; 3) Indoles bearing electron-withdrawing groups such as F, Cl, Br on the phenyl ring were favored to the reaction. A representative procedure for this reaction is as follows: To a solution of substituted indoles 1 or 4 (1 mmol) and dialkylphosphites 2 (2 mmol) in HOAc (3 mL) heated with oil bath (50℃), Mn(OAc)3 (3 mmol) was added in portions within 0.5 h, then, the mixture was allowed to stir further for 0.5 h. After removal of the most solvent under reduced pressure, 50 mL water was added to the residue and the mixture was extracted with EtOAc (20 mL×3). The combined organic layers were dried over anhydrous Na2SO4, filtered, concentrated under reduced pressure, and the residue was purified by flash silica-gel column chromatography (using mixture of petroleum ether/ethyl acetate as eluent from ratio of 20/1 to 1/2) to afford the desired 2- or 3-phosphonyl indoles 3 or 5.
  • 加载中
    1. [1]

      [1] Selected recent Mn(OAc)3-mediated reaction reviews: (a) Pan, X. Q.; Zou, J. P.; Yi, W. B.; Zhang, W. Tetrahedron 2015, 71, 7481. (b) Denes, F.; Pichowicz, M.; Povie, G.; Renaud, P. Chem. Rev. 2014, 114, 2587. (c) Mondal, M.; Bora, U. RSC Adv. 2013, 3, 18716. (d) Yan, G.; Yang, M.; Wu, X. Org. Biomol. Chem. 2013, 11, 7999. (e) Pan, X. Q.; Zou, J. P.; Zhang, W. Mol. Diversity 2009, 13, 421. (f) Snider, B. B. Tetrahedron 2009, 65, 10738. (g) Demir, A. S.; Emrullahoglu, M. Curr. Org. Synth. 2007, 4, 321. (h) Linker, T. J. Organomet. Chem. 2002, 661, 159. (i) Snider, B. B. Chem. Rev. 1996, 96, 339.

    2. [2]

      [2] Selected recent Mn(OAc)3-mediated reaction papers: (a) Castro, S.; Fernández, J. J.; Fañanás, F. J.; Vicente, R.; Rodríguez, F. Chem. Eur. J. 2016, 22, 9068. (b) Zhang, G. Y.; Li, C. K.; Li, D. P.; Zeng, R. S.; Shoberu, A.; Zou, J. P. Tetrahedron 2016, 72, 2972. (c) Chuang, C. P.; Chen, Y. J. Tetrahedron 2016, 721911. (d) Zhao, Y. Y.; Hu, Y. C.; Wang, H. L.; Li, X. C.; Wan, B. S. J. Org. Chem. 2016, 81, 4412. (e) Zhang, P. Z.; Li, C. K.; Zhang, G. Y.; Zhang, L.; Jiang, Y. J.; Zou, J. P. Tetrahedron 2016, 72, 3250. (f) Tejeda, J. E. C.; Landschoot, B. K.; Kerr, M. A. Org. Lett. 2016, 18, 2142. (g) Liu, X. G.; Chen, X. H.; Mohr, J. T. Chem. Eur. J. 2016, 22, 2274. (h) Lin, G. A.; Chuang, C. P. Tetrahedron 2015, 71, 4795. (i) Gao, Y. Z.; Li, X. Q.; Xu, J.; Wu, Y. L.; Chen, W. Z.; Tang, G.; Zhao, Y. F. Chem. Commun. 2015, 51, 1605. (j) Xu, J.; Li, X. Q.; Gao, Y. Z.; Zhang, L. L.; Chen, W. Z.; Fang, H.; Tang, G.; Zhao, Y. F. Chem. Commun. 2015, 51, 11240. (k) Xue, J. F.; Zhou, S. F.; Liu, Y. Y.; Pan, X. Q.; Zou, J. P.; Asekun, O. T. Org. Biomol. Chem. 2015, 13, 4896. (l) Zhou, S. F.; Li, D. P.; Liu, K.; Zou, J. P.; Asekun, O. T. J. Org. Chem. 2015, 80, 1214. (m) Lv, W. X.; Zeng, Y. F.; Zhang, S. S.; Li, Q. J.; Wang, H. G. Org. Lett. 2015, 17, 2972. (n) Zhang, F. Y.; Wang, L. M.; Zhang, C.; Zhao, Y. F. Chem. Commun. 2014, 50, 2046. (o) Nikishin, G. I. Adv. Synth. Catal. 2014, 356, 2266. (p) Fisher, H. C.; Berger, O.; Gelat, F.; Montchamp, J. L. Adv. Synth. Catal. 2014, 356, 1199. (q) Cao, J. J.; Wang, X.; Wang, S. Y.; Ji, S. J. Chem. Commun. 2014, 50, 12892. (r) Berger, O.; Montchamp, J. L. Chem. Eur. J. 2014, 20, 12385. (s) Gao, Y. Z.; Wu, J.; Xu, J.; Wang, X. R.; Tang, G.; Zhao, Y. F. Asian J. Org. Chem. 2014, 3, 691. (t) Li, Y.; Qiu, G.; Ding, Q.; Wu, J. Tetrahedron 2014, 70, 4652. (u) Alagoez, O.; Yilmaz, M.; Pekel, A. T.; Graiff, C.; Maggi, R. RSC Adv. 2014, 4, 14644. (v) Li, D. P.; Pan, X. Q.; An, L. T.; Zou, J. P.; Zhang, W. J. Org. Chem. 2014, 79, 1850. (w) He, S.; Yang, W.; Zhu, L.; Du, G.; Lee, C. S. Org. Lett. 2014, 16, 496. (x) Cao, X. H.; Pan, X. Q.; Zhou, P. J.; Zou, J. P.; Asekun, O. T. Chem. Commun. 2014, 50, 3359.

    3. [3]

      [3] (a) Gribble, G. W. Heterocyclic Scaffolds Ⅱ: Reactions and Applications of Indoles, Springer-Verlag, Berlin, Heidelberg, 2010, pp. 33~43. (b) Chen, F. E.; Huang, J. Chem. Rev. 2005, 105, 4671. (c) Sechi, M.; Derudas, M.; Dallocchio, R.; Dessi, A.; Bacchi, A.; Sannia, L.; Carta, F.; Palomba, M.; Ragab, O.; Chan, C.; Shoemaker, R.; Sei, S.; Dayam, R.; Neamati, N. J. Med. Chem. 2004, 47, 5298. (d) Li, Y. M.; Sun, M.; Wang, H. L.; Tian, Q. P.; Yang, S. D. Angew. Chem. 2013, 125, 4064. Angew. Chem. Int. Ed. 2013, 52, 3972.

    4. [4]

      [4] (a) Zhou, X. J.; Garner, R. C.; Nicholson, S. C.; Kissling, J.; Mayers, D.; J. Clin. Pharmacol. 2009, 49, 1408. (b) Alexandre, F. R.; Amador, A.; Bot, S.; Caillet, C.; Convard, T.; Jakubik, J.; Musiu, C.; Poddesu, B.; Vargiu, L.; Liuzzi, M.; Roland, A.; Seifer, M.; Standring, D.; Storer, R.; Dousson, C. B. J. Med. Chem. 2011, 54, 392. (c) Storer, R.; Dousson, C.; Alexandre, F. R.; Roland, A. WO 054182, 2006. (d) Zhou, X. J.; Pietropaolo, K.; Damphousse, D.; Belanger, B.; Chen, J.; Sullivan-Bólyai, J.; Mayers, D. Antimicrob. Agents Chemother. 2009, 53, 1739. (e) Regina, G. L.; Coluccia, A.; Silvestri, R. Antiviral Chem. Chemother. 2010, 20, 213; (f) Bisseret, P.; Thielges, S.; Bourg, S.; Miethke, M.; Marahiel, M. A.; Eustache, J. Tetrahedron Lett. 2007, 48, 6080.

    5. [5]

      [5] (a) Razumor, A. I.; Gurevich, P. A. J. Gen. Chem. USSR (Engl. Transl.) 1967, 37, 1532. (b) Issleib, K.; Wolff, R.; Lengies, M. J. Prakt. Chem. 1976, 318, 207. (c) Jiao, X. Y.; Xiong, F. G.; Chen, W. Y.; Hu, B. F. Chin. J. Org. Chem. 1994, 14, 622. (焦献云, 熊发高, 陈万义, 胡秉方, 有机化学, 1994, 14, 622.)

    6. [6]

      [6] (a) Thielges, S.; Meddah, E.; Bisseret, P.; Eustache, J. Tetrahedron Lett. 2004, 45, 907. (b) Kondoh, A.; Yorimitsu, H.; Oshima, K. Org. Lett. 2010, 12, 1476.

    7. [7]

      [7] For selected C-H functionalizations of indoles, see: (a) Lane, B. S.; Brown, M. A.; Sames, D. J. Am. Chem. Soc. 2005, 127, 8050. (b) Deprez, N. R.; Kalyani, D.; Krause, A.; Sanford, M. S. J. Am. Chem. Soc. 2006, 128, 4972. (c) Phipps, R. J.; Grimster, N. P.; Gaunt, M. J. J. Am. Chem. Soc. 2008, 130, 8172. (d) Hwang, S. J.; Cho, S. H.; Chang, S. J. Am. Chem. Soc. 2008, 130, 16158. (e) Lebrasseur, N.; Larrosa, I. J. Am. Chem. Soc. 2008, 130, 2926. (f) Yang, S. D.; Sun, C. L.; Fang, Z.; Li, B. J.; Li, Y. Z.; Shi, Z. J. Angew. Chem. 2008, 120, 1495. (g) Ding, S.; Shi, Z., Jiao, N. Org. Lett. 2010, 12, 1540. (h) Ding, S.; Jiao, N. J. Am. Chem. Soc. 2011, 133, 12374. (i) Liu, Q.; Li, G.; Yi, H.; Wu, P.; Liu, J.; Lei, A. Chem. Eur. J. 2011, 17, 2353. (j) Pan, S.; Ryu, N.; Shibata, T. J. Am. Chem. Soc. 2012, 134, 17474. (k) Jiao, L.; Herdtweck, E.; Bach, T. J. Am. Chem. Soc. 2012, 134, 14563. (l) Stahl, T.; Muther, K.; Ohki, Y.; Tatsumi, K.; Oestreich, M. J. Am. Chem. Soc. 2013, 135, 10978. (m) Lü, J.; Qin, Y.; Cheng, J. P.; Luo, S. Z. Acta Chim. Sinica 2014, 72, 809. (吕健, 秦岩, 程津培, 罗三中, 化学学报, 2014, 72, 809.); (n) Zhang, Q. C.; Lü, J.; Luo, S. Z. Acta Chim. Sinica 2016, 74, 61. (张启超, 吕健, 罗三中, 化学学报, 2016, 74, 61.); (o) Lu, Q. Q.; Yi, H.; Lei, A. W. Acta Chim. Sinica 2015, 73, 1245. (陆庆全, 易红, 雷爱文, 化学学报, 2015, 73, 1245.)

    8. [8]

      [8] (a) Zhang, H. J.; Lin, W. D.; Wu, Z. J.; Ruan, W. Q.; Wen, T. B. Chem. Commun. 2015, 51, 3450. (b) Mao, X.; Ma, X.; Zhang, S.; Hu, H.; Zhu, C. J.; Cheng, Y. X. Eur. J. Org. Chem. 2013, 20, 4245. (c) Xiang, C. B.; Bian, Y. J.; Mao, X. R.; Huang, Z. Z. J. Org. Chem. 2012, 77, 7706. (d) Kagayama, T.; Nakano, A.; Sakaguchi, S.; Ishii, Y. Org. Lett. 2006, 8, 407. (e) Zhang, B.; Daniliuc, C. G.; Studer, A. Org. Lett. 2014, 16, 250. (f) Wang, G. W.; Wang, C. Z.; Zou, J. P. J. Org. Chem. 2011, 76, 6088. (g) Li, L.; Wang, J. J.; Wang, G. W. J. Org. Chem. 2016, 81, 5433.

    9. [9]

      [9] (a) Benincori, T.; Piccolo, O.; Rizzo, S.; Sannicolo, F. J. Org. Chem. 2000, 65, 8340. (b) Wang, H. L.; Li, X. C.; Wu, F.; Wan, B. S. Synthesis 2012, 44, 941. (c) Zhou, A. X.; Mao, L. L.; Wang, G. W.; Yang, S. D. Chem. Commun. 2014, 50, 8529.

    10. [10]

      [10] (a) Chen, S. Y.; Zeng, R. S.; Zou, J. P.; Asekun, O. T. J. Org. Chem. 2014, 79, 1449. (b) Sun, W. B.; Ji, Y. F.; Pan, X. Q.; Zhou, S. F.; Zou, J. P.; Zhang, W.; Asekun, O. T. Synthesis 2013, 45, 1529. (c) Zhou, P.; Jiang, Y. J.; Zou, J. P.; Zhang, W. Synthesis 2012, 44, 1043. (d) Zhou, J.; Zhang, G. L.; Zou, J. P.; Zhang, W. Eur. J. Org. Chem. 2011, 19, 3412. (e) Pan, X. Q.; Wang, L.; Zou, J. P.; Zhang, W. Chem. Commun. 2011, 47, 7875. (f) Pan, X. Q.; Zou, J. P.; Wang, L.; Zhang, W. Chem. Commun. 2010, 46, 1721. (g) Xu, W.; Zou, J. P.; Zhang, W. Tetrahedron Lett. 2010, 51, 2639. (h) Mu, X. J.; Zou, J. P.; Qian, Q. F.; Zhang, W. Org. Lett. 2006, 8, 5291. (i) Mu, X. J.; Lei, M. Y.; Zou, J. P.; Zhang, W. Tetrahedron Lett. 2006, 47, 1125.

  • 加载中
    1. [1]

      Zhen Yao ,  Bing Lin ,  Youping Tian ,  Tao Li ,  Wenhui Zhang ,  Xiongwei Liu ,  Wude Yang . Visible-Light-Mediated One-Pot Synthesis of Secondary Amines and Mechanistic Exploration. University Chemistry, 2024, 39(5): 201-208. doi: 10.3866/PKU.DXHX202311033

    2. [2]

      Yunhao Zhang ,  Yinuo Wang ,  Siran Wang ,  Dazhen Xu . Progress in Selective Construction of Functional Aromatics from Nitrogenous Cycloalkanes. University Chemistry, 2024, 39(11): 136-145. doi: 10.3866/PKU.DXHX202401083

    3. [3]

      Lei Shi . Nucleophilicity and Electrophilicity of Radicals. University Chemistry, 2024, 39(11): 131-135. doi: 10.3866/PKU.DXHX202402018

    4. [4]

      Danqing Wu ,  Jiajun Liu ,  Tianyu Li ,  Dazhen Xu ,  Zhiwei Miao . Research Progress on the Simultaneous Construction of C—O and C—X Bonds via 1,2-Difunctionalization of Olefins through Radical Pathways. University Chemistry, 2024, 39(11): 146-157. doi: 10.12461/PKU.DXHX202403087

    5. [5]

      Jiajia Li ,  Xiangyu Zhang ,  Zhihan Yuan ,  Zhengyang Qian ,  Jian Zhu . 3D Printing Based on Photo-Induced Reversible Addition-Fragmentation Chain Transfer Polymerization. University Chemistry, 2024, 39(5): 11-19. doi: 10.3866/PKU.DXHX202309073

    6. [6]

      Zijian Zhao ,  Yanxin Shi ,  Shicheng Li ,  Wenhong Ruan ,  Fang Zhu ,  Jijun Jiang . A New Exploration of the Preparation of Polyacrylic Acid by Free Radical Polymerization Based on the Concept of Green Chemistry. University Chemistry, 2024, 39(5): 315-324. doi: 10.3866/PKU.DXHX202311094

    7. [7]

      Doudou Qin ,  Junyang Ding ,  Chu Liang ,  Qian Liu ,  Ligang Feng ,  Yang Luo ,  Guangzhi Hu ,  Jun Luo ,  Xijun Liu . Addressing Challenges and Enhancing Performance of Manganese-based Cathode Materials in Aqueous Zinc-Ion Batteries. Acta Physico-Chimica Sinica, 2024, 40(10): 2310034-. doi: 10.3866/PKU.WHXB202310034

    8. [8]

      Yingchun ZHANG , Yiwei SHI , Ruijie YANG , Xin WANG , Zhiguo SONG , Min WANG . Dual ligands manganese complexes based on benzene sulfonic acid and 2, 2′-bipyridine: Structure and catalytic properties and mechanism in Mannich reaction. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1501-1510. doi: 10.11862/CJIC.20240078

    9. [9]

      Jinyao Du ,  Xingchao Zang ,  Ningning Xu ,  Yongjun Liu ,  Weisi Guo . Electrochemical Thiocyanation of 4-Bromoethylbenzene. University Chemistry, 2024, 39(6): 312-317. doi: 10.3866/PKU.DXHX202310039

    10. [10]

      Shipeng WANG , Shangyu XIE , Luxian LIANG , Xuehong WANG , Jie WEI , Deqiang WANG . Piezoelectric effect of Mn, Bi co-doped sodium niobate for promoting cell proliferation and bacteriostasis. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1919-1931. doi: 10.11862/CJIC.20240094

    11. [11]

      Chengqian Mao ,  Yanghan Chen ,  Haotong Bai ,  Junru Huang ,  Junpeng Zhuang . Photodimerization of Styrylpyridinium Salt and Its Application in Silk Screen Printing. University Chemistry, 2024, 39(5): 354-362. doi: 10.3866/PKU.DXHX202312014

    12. [12]

      Yinuo Wang ,  Siran Wang ,  Yilong Zhao ,  Dazhen Xu . Selective Synthesis of Diarylmethyl Anilines and Triarylmethanes via Multicomponent Reactions: Introduce a Comprehensive Experiment of Organic Chemistry. University Chemistry, 2024, 39(8): 324-330. doi: 10.3866/PKU.DXHX202401063

    13. [13]

      Changyan Sun ,  Hualei Zhou ,  Bin Dong . Application of “PBL” Teaching Mode in Inorganic Chemistry Experimental Education in the Perspective of Course Ideology and Politics: Taking Preparation of Manganese Carbonate as an Example. University Chemistry, 2024, 39(11): 378-383. doi: 10.12461/PKU.DXHX202402016

    14. [14]

      Wentao Lin ,  Wenfeng Wang ,  Yaofeng Yuan ,  Chunfa Xu . Concerted Nucleophilic Aromatic Substitution Reactions. University Chemistry, 2024, 39(6): 226-230. doi: 10.3866/PKU.DXHX202310095

    15. [15]

      Heng Zhang . Determination of All Rate Constants in the Enzyme Catalyzed Reactions Based on Michaelis-Menten Mechanism. University Chemistry, 2024, 39(4): 395-400. doi: 10.3866/PKU.DXHX202310047

    16. [16]

      Yuting Zhang ,  Zhiqian Wang . Methods and Case Studies for In-Depth Learning of the Aldol Reaction Based on Its Reversible Nature. University Chemistry, 2024, 39(7): 377-380. doi: 10.3866/PKU.DXHX202311037

    17. [17]

      Ruitong Zhang ,  Zhiqiang Zeng ,  Xiaoguang Zhang . Improvement of Ethyl Acetate Saponification Reaction and Iodine Clock Reaction Experiments. University Chemistry, 2024, 39(8): 197-203. doi: 10.3866/PKU.DXHX202312004

    18. [18]

      Lu XU , Chengyu ZHANG , Wenjuan JI , Haiying YANG , Yunlong FU . Zinc metal-organic framework with high-density free carboxyl oxygen functionalized pore walls for targeted electrochemical sensing of paracetamol. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 907-918. doi: 10.11862/CJIC.20230431

    19. [19]

      Honglian Liang ,  Xiaozhe Kuang ,  Fuping Wang ,  Yu Chen . Exploration and Practice of Integrating Ideological and Political Education into Physical Chemistry: a Case on Surface Tension and Gibbs Free Energy. University Chemistry, 2024, 39(10): 433-440. doi: 10.12461/PKU.DXHX202405073

    20. [20]

      Yuan Chun ,  Lijun Yang ,  Jinyue Yang ,  Wei Gao . Ideological and Political Design of BZ Oscillatory Reaction Experiment. University Chemistry, 2024, 39(2): 72-76. doi: 10.3866/PKU.DXHX202308072

Get Citation
PDF
XML
Metrics
  • PDF Downloads(0)
  • Abstract views(337)
  • HTML views(25)

通讯作者: 陈斌, bchen63@163.com
  • 1. 

    沈阳化工大学材料科学与工程学院 沈阳 110142

  1. 本站搜索
  2. 百度学术搜索
  3. 万方数据库搜索
  4. CNKI搜索
Address：Zhongguancun North First Street 2,100190 Beijing, PR China Tel: +86-010-82449177-888
Powered By info@rhhz.net

/

DownLoad:  Full-Size Img  PowerPoint
Return