Synthesis 2016; 48(16): 2671-2678
DOI: 10.1055/s-0035-1562516
special topic
© Georg Thieme Verlag Stuttgart · New York

Construction of Polycyclic Fused Pyrrolidines with Three Contiguous Stereocenters via Michael Addition of Vinylmalononitriles to Nitrostyrenes­ Using l-Proline-Derived Thiourea

Manjunatha Vishwanath
Chemical Biology Laboratory, Department of Biotechnology, Bhupat and Jyoti Mehta School of Biosciences Building, Indian Institute of Technology Madras, Chennai 600036, India   Email: vkesavan@iitm.ac.in
,
Muthuraj Prakash
Chemical Biology Laboratory, Department of Biotechnology, Bhupat and Jyoti Mehta School of Biosciences Building, Indian Institute of Technology Madras, Chennai 600036, India   Email: vkesavan@iitm.ac.in
,
Poopathy Vinayagam
Chemical Biology Laboratory, Department of Biotechnology, Bhupat and Jyoti Mehta School of Biosciences Building, Indian Institute of Technology Madras, Chennai 600036, India   Email: vkesavan@iitm.ac.in
,
Venkitasamy Kesavan*
Chemical Biology Laboratory, Department of Biotechnology, Bhupat and Jyoti Mehta School of Biosciences Building, Indian Institute of Technology Madras, Chennai 600036, India   Email: vkesavan@iitm.ac.in
› Author Affiliations
Further Information

Publication History

Received: 31 May 2016

Accepted after revision: 22 June 2016

Publication Date:
29 July 2016 (eFirst)

Abstract

The catalytic efficiency of a bifunctional chiral thiourea derived from l-proline was evaluated in the asymmetric direct vinylogous Michael reaction of α,α-dicyanoolefins to β-nitrostyrenes with an electron-releasing or electron-withdrawing substituent in various positions. The corresponding adducts were isolated in good yields, with excellent diastereo- (>99%) and enantioselectivity (up to 95%). The Michael adducts were further functionalized to achieve the synthesis of polycyclic fused pyrrolidines with three contiguous stereocenters in good enantioselectivities.

Supporting Information

 
  • References

    • 1a Beghyn T, Deprez-Poulain R, Willand N, Folleas B, Deprez B. Chem. Biol. Drug Des. 2008; 72: 3
    • 1b Kaushik NK, Kaushik N, Attri P, Kumar N, Kim CH, Verma AK, Choi EH. Molecules 2013; 18: 6620
    • 1c Vitaku E, Smith DT, Njardarson JT. J. Med. Chem. 2014; 57: 10257
    • 2a Buarque CD, Salustiano EJ, Fraga KC, Alves BR. M, Costa PR. R. Eur. J. Med. Chem. 2014; 78: 190
    • 2b Arumugam N, Raghunathan R, Almansour AI, Karama U. Bioorg. Med. Chem. Lett. 2012; 22: 1375
    • 2c Buarque CD, Militao GC. G, Lima DJ. B, Costa-Lotufo LV, Pessoa C, Odorico de Moraes M, Cunha-Junior EF, Torres-Santos EC, Netto CD, Costa PR. R. Bioorg. Med. Chem. 2011; 19: 6885
    • 3a Zhou Y, Zhu Y, Yan S, Gong Y. Angew. Chem. Int. Ed. 2013; 52: 10265
    • 3b Hornillos V, Perez M, Fananas-Mastral M, Feringa BL. J. Am. Chem. Soc. 2013; 135: 2140
    • 3c Nie J, Hua M.-Q, Xiong H.-Y, Zheng Y, Ma J.-A. J. Org. Chem. 2012; 77: 4209
    • 4a Trost BM, Crawley ML. Chem. Rev. 2003; 103: 2921
    • 4b Trost BM. J. Org. Chem. 2004; 69: 5813
    • 4c Cui H.-L, Chen Y.-C. Chem. Commun. 2009; 4479
    • 4d Shi X.-M, Dong W.-P, Zhu L.-P, Jiang X.-X, Wang R. Adv. Synth. Catal. 2013; 355: 3119
    • 5a Xue D, Li J, Zhang Z.-T, Deng J.-G. J. Org. Chem. 2007; 72: 5443
    • 5b Trost BM, Hitce J. J. Am. Chem. Soc. 2009; 131: 4572
    • 5c Bencivenni G, Galzerano P, Mazzanti A, Bartoli G, Melchiorre P. Proc. Natl. Acad. Sci. U.S.A. 2010; 107: 20642
    • 5d Shepherd NE, Tanabe H, Xu Y, Matsunaga S, Shibasaki M. J. Am. Chem. Soc. 2010; 132: 3666
    • 5e Curti C, Rassu G, Zambrano V, Pinna L, Pelosi G, Sartori A, Battistini L, Zanardi F, Casiraghi G. Angew. Chem. Int. Ed. 2012; 51: 6200
    • 5f Manna MS, Kumar V, Mukherjee S. Chem. Commun. 2012; 48: 5193
    • 5g Zhang J, Liu X, Ma X, Wang R. Chem. Commun. 2013; 49: 9329
    • 6a Xue D, Chen Y.-C, Wang Q.-W, Cun L.-F, Zhu J, Deng J.-G. Org. Lett. 2005; 7: 5293
    • 6b Poulsen TB, Bell M, Jørgensen KA. Org. Biomol. Chem. 2006; 4: 63
    • 6c Chen W.-Y, Ouyang L, Chen R.-Y, Li X.-S. Synth. Commun. 2012; 42: 2585
    • 6d Jiang L, Zheng H.-T, Liu T.-Y, Yue L, Chen Y.-C. Tetrahedron 2007; 63: 5123
    • 7a Vishwanath M, Vinayagam P, Gajulapalli VP. R, Kesavan V. Asian J. Org. Chem. 2016; 5: 613
    • 7b Muthusamy S, Prakash M, Ramakrishnan C, Gromiha MM, Kesavan V. ChemCatChem 2016; 8: 1708
    • 7c Kumarswamyreddy N, Kesavan V. Org. Lett. 2016; 18: 1354
    • 8a Jayakumar S, Muthusamy S, Prakash M, Kesavan V. Eur. J. Org. Chem. 2014; 1893
    • 8b Gajulapalli VP. R, Vinayagam P, Kesavan V. Org. Biomol. Chem. 2014; 12: 4186
    • 8c Vinayagam P, Vishwanath M, Kesavan V. Tetrahedron: Asymmetry 2014; 25: 568
    • 8d Gajulapalli VP. R, Vinayagam P, Kesavan V. RSC Adv. 2015; 5: 7370
  • 9 Zhou L.-H, Wang N, Chen G.-N, Yang Q, Yang S.-Y, Zhang W, Zhang Y, Yu X.-Q. J. Mol. Catal. B: Enzym. 2014; 109: 170