Synlett 2015; 26(20): 2821-2825
DOI: 10.1055/s-0035-1560500
cluster
© Georg Thieme Verlag Stuttgart · New York

Copper-Catalyzed Synthesis of Furo[3,2-c]coumarins and Dihydrofuro[3,2-c]coumarins through a Propargylation/Alkyne Oxacyclization/Isomerization Cascade under Microwave Irradiation

Xiao-Yan Zhang
a  Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Department of Chemistry and Life Science, Zhejiang Normal University, Jinhua 321004, P. R. of China   Email: xiejw@zjnu.cn
b  International Academy of Targeted Therapeutics and Innovation, Chongqing University of Arts and Sciences, 319 Honghe Ave., Yongchuan, Chongqing 402160, P. R. of China   Email: cuihailei616@163.com
,
Li-Li Hu
b  International Academy of Targeted Therapeutics and Innovation, Chongqing University of Arts and Sciences, 319 Honghe Ave., Yongchuan, Chongqing 402160, P. R. of China   Email: cuihailei616@163.com
,
Ze Shen
b  International Academy of Targeted Therapeutics and Innovation, Chongqing University of Arts and Sciences, 319 Honghe Ave., Yongchuan, Chongqing 402160, P. R. of China   Email: cuihailei616@163.com
,
Zhong-Zhu Chen
b  International Academy of Targeted Therapeutics and Innovation, Chongqing University of Arts and Sciences, 319 Honghe Ave., Yongchuan, Chongqing 402160, P. R. of China   Email: cuihailei616@163.com
,
Zhi-Gang Xu
b  International Academy of Targeted Therapeutics and Innovation, Chongqing University of Arts and Sciences, 319 Honghe Ave., Yongchuan, Chongqing 402160, P. R. of China   Email: cuihailei616@163.com
,
Shi-Qiang Li
b  International Academy of Targeted Therapeutics and Innovation, Chongqing University of Arts and Sciences, 319 Honghe Ave., Yongchuan, Chongqing 402160, P. R. of China   Email: cuihailei616@163.com
,
Jian-Wu Xie*
a  Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Department of Chemistry and Life Science, Zhejiang Normal University, Jinhua 321004, P. R. of China   Email: xiejw@zjnu.cn
,
Hai-Lei Cui*
b  International Academy of Targeted Therapeutics and Innovation, Chongqing University of Arts and Sciences, 319 Honghe Ave., Yongchuan, Chongqing 402160, P. R. of China   Email: cuihailei616@163.com
› Author Affiliations
Further Information

Publication History

Received: 21 July 2015

Accepted after revision: 21 September 2015

Publication Date:
13 October 2015 (online)


Abstract

A novel copper-catalyzed microwave-promoted propargyl­ation/alkyne oxacyclization/isomerization cascade for the synthesis of 2-methylfuro[3,2-c]coumarins has been developed. This reaction provides furo[3,2-c]coumarins in moderate to good yields (≤82%) from readily available 4-hydroxycoumarins and terminal propargyl acetates as starting materials. Interestingly, by changing the solvent from dimethyl sulfoxide to 1,2-dichloroethane, the isomeric series of 2-meth­ylene-2,3-dihydrofuro[3,2-c]coumarins were obtained in good to acceptable yields (≤85%).

Supporting Information

 
  • References and Notes

    • 1a Lee K.-H. J. Nat. Prod. 2010; 73: 500
    • 1b Boland GM, Donnelly DM. X. Nat. Prod. Rep. 1998; 15: 241
    • 2a Wang X, Bastow KF, Sun C.-M, Lin Y.-L, Yu H.-J, Don M.-J, Wu T.-S, Nakamura S, Lee K.-H. J. Med. Chem. 2004; 47: 5816
    • 2b Wang X, Nakagawa-Goto K, Bastow KF, Don M.-J, Lin Y.-L, Wu T.-S, Lee K.-H. J. Med. Chem. 2006; 49: 5631
    • 2c Dong Y, Shi Q, Liu Y.-N, Wang X, Bastow KF, Lee K.-H. J. Med. Chem. 2009; 52: 3586
    • 2d Dong Y, Shi Q, Pai H.-C, Peng C.-Y, Pan S.-L, Teng C.-M, Nakagawa-Goto K, Yu D, Liu Y.-N, Wu P.-C, Bastow KF, Morris-Natschke SL, Brossi A, Lang J.-Y, Hsu JL, Hung M.-C, Lee K.-H. J. Med. Chem. 2010; 53: 2299
    • 3a Cadierno V, Díez J, Gimeno J, Nebra N. J. Org. Chem. 2008; 73: 5852
    • 3b Lee C.-J, Jang Y.-J, Wu Z.-Z, Lin W. Org. Lett. 2012; 14: 1906
    • 3c Zhang WL, Yue SN, Shen YM, Hu HY, Meng Q.-H, Wu H, Liu Y. Org. Biomol. Chem. 2015; 13: 3602
    • 3d Cheng G, Hu Y. J. Org. Chem. 2008; 73: 4732
    • 3e Huang W, Wang J, Shen Q, Zhou X. Tetrahedron 2007; 63: 11636
    • 3f Ponra S, Gohain M, van Tonder JH, Bezuidenhoudt BC. B. Synlett 2015; 26: 745

      For reviews on cascade reactions, see:
    • 4a Grondal C, Jeanty M, Enders D. Nat. Chem. 2010; 2: 167
    • 4b Yu X, Wang W. Org. Biomol. Chem. 2008; 6: 2037
    • 4c Enders D, Grondal C, Hüttl MR. M. Angew. Chem. Int. Ed. 2007; 46: 1570
    • 4d Walji AM, MacMillan DW. C. Synlett 2007; 1477
    • 4e Nicolaou KC, Edmonds DJ, Bulger PG. Angew. Chem. Int. Ed. 2006; 45: 7134

      For reviews on propargylation, see:
    • 5a Ding C.-H, Hou X.-L. Chem. Rev. 2011; 111: 1914
    • 5b Miyake Y, Uemura S, Nishibayashi Y. ChemCatChem 2009; 1: 342
    • 5c Detz RJ, Hiemstra H, van Maarseveen JH. Eur. J. Org. Chem. 2009; 6263
    • 5d Nishibayashi Y. Synthesis 2012; 44: 489
    • 5e Zhang D.-Y, Hu X.-P. Tetrahedron Lett. 2015; 56: 283
    • 5f Hu X.-H, Liu Z.-T, Shao L, Hu X.-P. Synthesis 2015; 47: 913

      For selected examples on the synthesis of furan derivatives by using a propargylation/cycloisomerization strategy, see:
    • 6a Cadierno V, Gimeno J, Nebra N. Adv. Synth. Catal. 2007; 349: 382
    • 6b Yoshida M, Ohno S, Shishido K. Chem. Eur. J. 2012; 18: 1604
    • 6c Pan Y.-m, Zhao S.-y, Ji W.-h, Zhang Z.-p. J. Comb. Chem. 2009; 11: 103
    • 6d Zhan Z.-p, Cai X.-b, Wang S.-p, Yu J.-l, Liu H.-j, Cui Y.-y. J. Org. Chem. 2007; 72: 9838
    • 6e Suhre MH, Reif M, Kirsch SF. Org. Lett. 2005; 7: 3925
    • 6f Sanz R, Miguel D, Martínez A, Álvarez-Gutiérrez JM, Rodríguez F. Org. Lett. 2007; 9: 727
    • 6g Feng X, Tan Z, Chen D, Shen Y, Cuo C.-C, Xiang J, Zhu C. Tetrahedron Lett. 2008; 49: 4110

      For reviews, see:
    • 7a Larhed M, Moberg C, Hallberg A. Acc. Chem. Res. 2002; 35: 717
    • 7b Roberts BA, Strauss CR. Acc. Chem. Res. 2005; 38: 653
    • 7c Lew A, Krutzik PO, Hart ME, Chamberlin AR. J. Comb. Chem. 2002; 4: 95
    • 7d Lidström P, Tierney J, Wathey B, Westman J. Tetrahedron 2001; 57: 9225
    • 7e Perreux L, Loupy A. Tetrahedron 2001; 57: 9199
  • 8 Higher temperatures and greater catalyst loadings led to the formation of dihydrofuro[3,2-c]coumarin 4g in 41% yield (see Scheme 3).
    • 9a Shiner VJ, Wilson JW. J. Am. Chem. Soc. 1962; 84: 2402
    • 9b Imada Y, Yuasa M, Nakamura I, Murahashi S.-I. J. Org. Chem. 1994; 59: 2282
  • 10 For a review, see: Lipshutz BH. Chem. Rev. 1986; 86: 795
  • 11 For a review, see: Musa MA, Cooperwood JS, Khan OF. Curr. Med. Chem. 2008; 15: 2664
  • 12 For a recent example of an asymmetric synthesis of dihydrofurans from propargylic esters, see: Zhu F.-L, Wang Y.-H, Zhang D.-Y, Xu J, Hu X.-P. Angew. Chem. Int. Ed. 2014; 53: 10223

    • For studies on the synthesis of dihydrofuro[3,2-c]coumarins by the Xie group, see:
    • 13a Xie J.-W, Li P, Wang T, Zhou F.-T. Tetrahedron Lett. 2011; 52: 2379
    • 13b Fan L.-P, Li P, Li X.-S, Xu D.-C, Ge M.-M, Zhu W.-D, Xie J.-W. J. Org. Chem. 2010; 75: 8716
  • 14 In this case, the isomerized product 3m was isolated in 91% yield.
  • 15 Furo[3,2-c]coumarins 3; General Procedure A mixture of 4-hydroxycoumarin 1 (0.48 mmol, 1.2 equiv), propargyl acetate 2 (0.40 mmol, 1.0 equiv), DIPEA (0.40 mmol, 1.0 eq), CuBr (0.02 mmol, 5 mol%), and DMSO (1 mL) was stirred at r.t. for 30 s and then heated at 100 °C for 20 min by microwave irradiation. The mixture was then cooled to r.t., the reaction was quenched with sat. aq NH4Cl, and the mixture was extracted with CH2Cl2. The organic layers were combined, washed with brine, dried (Na2SO4), filtered, and concentrated in vacuo. Purification by a flash chromatography (silica gel, hexane–EtOAc) gave the desired product 3.
  • 16 2-Methylene-2,3-dihydrofuro[3,2-c]coumarins 4; General Procedure A mixture of 4-hydroxycoumarin 1 (0.48 mmol, 1.2 equiv), propargyl acetate 2 (0.40 mmol, 1.0 equiv), DIPEA (0.40 mmol, 1.0 equiv), CuBr (0.02 mmol, 5 mol%), and DCE (1 mL) was stirred at r.t. for 30 s and then heated at 100 °C for 20 min by microwave irradiation. The mixture was cooled to r.t. and directly purified by flash chromatography (silica gel, hexane–EtOAc) to give the desired product 4.