Synlett 2014; 25(16): 2260-2264
DOI: 10.1055/s-0034-1378897
cluster
© Georg Thieme Verlag Stuttgart · New York

Tandem Diels–Alder [4+2] Cycloadditions and Intramolecular [3+2] Cross-Cycloadditions of Dienylcyclopropane 1,1-Diesters

Jun Ren
State Key Laboratory and Institute of Elemento-Organic Chemistry, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Nankai University, 94 Weijin Road, Tianjin 300071, P. R. of China   Email: wzwrj@nankai.edu.cn
,
Jilai Bao
State Key Laboratory and Institute of Elemento-Organic Chemistry, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Nankai University, 94 Weijin Road, Tianjin 300071, P. R. of China   Email: wzwrj@nankai.edu.cn
,
Weiwei Ma
State Key Laboratory and Institute of Elemento-Organic Chemistry, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Nankai University, 94 Weijin Road, Tianjin 300071, P. R. of China   Email: wzwrj@nankai.edu.cn
,
Zhongwen Wang*
State Key Laboratory and Institute of Elemento-Organic Chemistry, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Nankai University, 94 Weijin Road, Tianjin 300071, P. R. of China   Email: wzwrj@nankai.edu.cn
› Author Affiliations
Further Information

Publication History

Received: 12 May 2014

Accepted after revision: 30 July 2014

Publication Date:
09 September 2014 (online)


Abstract

A novel tandem reaction by combination of Diels–Alder [4+2] cycloaddition and [3+2] IMCC (intramolecular cross-cyclo­addition) of dienylcyclopropane 1,1-diesters has been successfully developed. In this reaction, three new rings and four new stereocenters were generated in one-pot. This supplies a strategy for rapid construction of 6,6- and 6,7-fused carbocyclic skeletons which are common cores in many biologically important natural products.

Supporting Information

 
  • References and Notes

    • 2a Sun H, Li S. Diterpenoid Chemistry . Chemical Industry Press; Beijing: 2011
    • 2b Shi YP. Mono- and Sesquiterpenoid Chemistry 2008;
    • 2c Wang FP. Alkaloid Chemistry . Chemical Industry Press; Beijing: 2008
    • 2d Breitmaier E. Terpenes: Flavors, Fragrances, Pharmaca, Pheromones. Wiley-VCH; Weinheim: 2006
    • 2e Sell CS. A Fragrant Introduction to Terpenoid Chemistry 2003

    • Platensymecin:
    • 2f Saleem M, Hussain H, Ahmed I, van Ree T, Krohn K. Nat. Prod. Rep. 2011; 28: 1534
    • 2g Tiefenbacher K, Mulzer J. Angew. Chem. Int. Ed. 2008; 47: 2548
    • 2h Yao YS, Yao ZJ. Chin. J. Org. Chem. 2008; 28: 1553
    • 2i Kauranoid Lungshengenin D: Jiang B, Lu Z.-Q, Hou A.-J, Zhao Q.-S, Sun H.-D. J. Nat. Prod. 1999; 62: 941

    • Icetexane:
    • 2j Simmons EM, Sarpong R. Nat. Prod. Rep. 2009; 26: 1195

    • Cyathane:
    • 2k Enquist JA. Jr, Stoltz BM. Nat. Prod. Rep. 2009; 26: 661

    • Eudesmane:
    • 2l Sanz JF, Marco JA. Phytochem. 1990; 29: 2913
    • 2m Cabrera E, Garcia-Granados A, Quecuty MA. Phytochem. 1988; 27: 183
    • 2n Bohlmann F, Ziesche J, King RM, Robinson H. Phytochem. 1981; 20: 751

    • Clerodane:
    • 2o Merritt AT, Ley SV. Nat. Prod. Rep. 1992; 9: 243
    • 3a Zhu W, Fang J, Liu Y, Ren J, Wang Z. Angew. Chem. Int. Ed. 2013; 52: 2032
    • 3b Wang Z, Ren J, Wang Z. Org. Lett. 2013; 15: 5682
    • 3c Bai Y, Tao W, Ren J, Wang Z. Angew. Chem. Int. Ed. 2012; 51: 4112
    • 3d Xing S, Li Y, Li Z, Liu C, Ren J, Wang Z. Angew. Chem. Int. Ed. 2011; 50: 12605
    • 3e Xing S, Pan W, Liu C, Ren J, Wang Z. Angew. Chem. Int. Ed. 2010; 49: 3215
    • 3f Hu B, Xing S, Ren J, Wang Z. Tetrahedron 2010; 66: 5671
    • 3g For a review of our research in this area, please see ref. 4c.

      For reviews on donor-acceptor cyclopropanes, see:
    • 4a Cavitt MA, Phun LH, France S. Chem. Soc. Rev. 2014; 43: 804
    • 4b Wang Y, Yin JJ. Chem. Reagents 2013; 35: 318
    • 4c Wang Z. Synlett 2012; 23: 2311
    • 4d Tang P, Qin Y. Synthesis 2012; 44: 2969
    • 4e Mel’nikov MY, Budynina EM, Ivanova OA, Trushkov IV. Mendeleev Commun. 2011; 21: 293
    • 4f Campbell MJ, Johnson JS, Parsons AT, Pohlhaus PD, Sanders SD. J. Org. Chem. 2010; 75: 6317
    • 4g Lebold TP, Kerr MA. Pure Appl. Chem. 2010; 82: 1797
    • 4h Carson CA, Kerr MA. Chem. Soc. Rev. 2009; 38: 3051
    • 4i De Simone F, Waser J. Synthesis 2009; 3353
    • 4j Agrawal D, Yadav VK. Chem. Commun. 2008; 6471
    • 4k Yu M, Pagenkopf BL. Tetrahedron 2005; 61: 321
    • 4l Reissig H.-U, Zimmer R. Chem. Rev. 2003; 103: 1151
    • 4m Kulinkovich OG. Russ. Chem. Rev. 1993; 62: 839
    • 4n Wong HN. C, Hon M.-Y, Tse C.-W, Yip Y, Tanko J, Hudlicky T. Chem. Rev. 1989; 89: 165
    • 4o Wenkert E. Acc. Chem. Res. 1980; 13: 27
    • 4p Danishefsky S. Acc. Chem. Res. 1979; 21: 66
  • 5 For an intermolecular [3+2] cycloaddition of an iron complex of dienylcyclopropane 1,1-diester with carbonyls, see: Christie SD. R, Cummins J, Elsegood MR. J, Dawson G. Synlett 2009; 257
  • 6 Other Lewis acids could also promote the [3+2] IMCC, among which Sc(OTf)3 behaved as the optimal one.
  • 7 CCDC 875497 (4a) contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk /data_request/cif.
  • 8 When dienylcyclopropane 1,1-diesters (1a or 1e) as a mixture of Z/E-isomers reacted with dienophiles, the ratio of Z/E-isomers increased as the reaction proceeded, which indicated that the E-isomers showed better reactivity than the Z-isomers.
  • 9 Typical Procedure A; Two-Stage Process: In a 25-mL tube were added dienylcyclopropane 1,1-diester 1a (88 mg, 0.39 mmol), MVK (2b; 0.5 mL, 7.86 mmol), p-hydroquinone (10 mg, 0.091 mmol) and toluene (3 mL) under N2. The tube was sealed and the reaction was carried out in an oil bath (120 °C). After complete consumption of 1a (monitored by TLC), the mixture was concentrated. Sc(OTf)3 (19 mg, 0.0384 mmol, 20 mol%) and DCE (4 mL) were then added, and the mixture was stirred at r.t. under an atmosphere of nitrogen until the reaction was complete (monitored by TLC). The solvent was evaporated under vacuum and the residue was purified by silica gel column chromatography to afford 4b (35% yield based on 1a, dr = 5:1). 1H NMR (400 MHz, CDCl3): δ = 5.66 (dd, J = 7.5, 2.1 Hz, 1 H), 5.45–5.54 (m, 1 H), 4.47 (d, J = 7.4 Hz, 1 H), 3.78 (s, 3 H), 3.75 (s, 3 H), 2.79 (dd, J = 13.5, 7.9 Hz, 1 H), 2.45 (d, J = 13.5 Hz, 1 H), 2.12–2.21 (m, 1 H), 2.11–2.01 (m, 3 H), 1.77 (d, J = 1.5 Hz, 1 H), 1.57–1.68 (m, 2 H), 1.41–1.50 (m, 1 H), 1.34 (s, 3 H). 13C NMR (101 MHz, CDCl3): δ = 172.51, 170.49, 130.05, 126.77, 86.68, 74.79, 68.14, 52.73, 52.61, 39.48, 38.09, 34.56, 29.06, 25.90, 20.10, 19.15. HRMS (ESI): m/z [M + Na]+ calcd for C16H22O5: 317.1359; found: 317.1360.
  • 10 Typical Procedure B; Domino Process: In a 25-mL tube were added dienylcyclopropane 1,1-diester 1f (102 mg, 0.39 mmol), MVK (2b; 0.5 mL, 7.86 mmol), p-hydroquinone (10 mg, 0.091 mmol) and toluene (3 mL) in N2. The tube was sealed and the reaction was carried out in an oil bath (120 °C). After completion of the reaction (monitored by TLC), the solvent was evaporated under vacuum and the residue was purified by silica gel column chromatography to afford 4i (51% based on 1f, dr = 20:1). 1H NMR (400 MHz, CDCl3): δ = 7.28–7.35 (m, 4 H), 7.23 (dd, J = 5.2, 3.3 Hz, 1 H), 6.01 (d, J = 3.4 Hz, 1 H), 4.34–4.39 (m, 1 H), 3.80 (s, 3 H), 3.74 (s, 3 H), 2.39–2.56 (m, 4 H), 2.16–2.25 (m, 2 H), 1.65–1.79 (m, 2 H), 1.60 (s, 3 H). 13C NMR (101 MHz, CDCl3): δ = 170.90, 140.27, 128.22, 126.78, 125.09, 124.93, 90.08, 81.41, 66.27, 52.64, 44.60, 41.70, 41.03, 25.13, 24.13, 14.72. HRMS (ESI): m/z [M + H]+ calcd for C21H24O5: 357.1697; found: 357.1702.