IJOC  Vol.2 No.1 , March 2012
Facile Synthesis of Novel Chiral Bicyclic Thioureas and Their Crystal Structures
Abstract: The novel well-defined chiral bicyclic thioureas based on enantiopure unsymmetric cis-2,5-disustituted pyrrolidine skeleton were firstly synthesized and fully characterized by their 1H NMR, 13C NMR and HRMS. Their absolute configurations were also determined by single-crystal X-ray analysis.
Cite this paper: P. An Wang, H. Fang Nie, L. Jie Yan and S. Yong Zhang, "Facile Synthesis of Novel Chiral Bicyclic Thioureas and Their Crystal Structures," International Journal of Organic Chemistry, Vol. 2 No. 1, 2012, pp. 15-20. doi: 10.4236/ijoc.2012.21003.

[1]   Z. Chai and G. Zhao, “Efficient Organocatalysts Derived from Simple Chiral Acyclic Amino Acids in Asymmetric Catalysis,” Catalysis Science & Technology, Vol. 2, No. 1, 2012, pp. 29-41. doi:10.1039/c1cy00347j

[2]   S. Varga, G. Jakab, L. Drahos, T. Holczbauer, M. Czugler and T. Soós, “Double Diastereo control in Bifunctional Thiourea Organocatalysis: Iterative Michael-Michael- Henry Sequence Regulated by the Configuration of Chiral Catalysts,” Organic Letters, Vol. 13, No. 20, 2011, pp. 5416-5419. doi:10.1021/ol201559j

[3]   Y. M. Lee, R. S. Klausen and E. N. Jacobsen, “Thiourea-Catalyzed Enan-tioselective Iso-Pictet-Spengler Reactions,” Organic Letters, Vol. 13, No. 20, 2011, pp. 5564- 5567. doi:10.1021/ol202300t

[4]   K. Hu, T. Liu, A. D. Lu, Y. Liu, Y. Wang, G. Wu, Z. Zhou and C. Tang, “Chiral Thiourea-Catalyzed Asymmetric Michael Addition of β-Oxo Phosphonate to Nitro Olefins: Convenient Synthesis of Optically Active β-Oxo Phosphonates,” European Journal of Organic Chemistry, Vol. 2011, No. 19, 2011, pp. 3507-3513. doi:10.1002/ejoc.201100029

[5]   N. Jia, J. Huang, L. Peng, L. L. Wang, J. F. Bai, F. Tian, G. Y. He, X. Y. Xu and L. X. Wang, “Asymmetric Hydroxyamination of Oxindoles Catalyzed by Chiral Bifunctional Tertiary Amine Thiourea: Construction of 3-Amino-2-oxindoles with Quaternary Stereocenters,” Organic & Biomolecular Chemistry, Vol. 10, No. 2, 2012, pp. 236-239. doi:10.1039/c1ob06413d

[6]   M. S. Taylor and E. N. Jacobsen, “Asymmetric Catalysis by Chiral Hydrogen-Bond Donors,” Angewandte Chemie International Edition, Vol. 45, No. 10, 2006, pp. 1520- 1543. doi:10.1002/anie.200503132

[7]   A. G. Doyle and E. N. Jacobsen, “Small-Molecule H-Bond Donors in Asymmetric Catalysis,” Chemical Reviews, Vol. 107, No. 12, 2007, pp. 5713-5743. doi:10.1021/cr068373r

[8]   R. R. Knowles and E. N. Jacobsen, “Attractive Noncovalent Interactions in Asymmetric Catalysis: Links between Enzymes and Small Molecule Catalysts,” PNAS, Vol. 107, No. 48, 2010, pp. 20678-20685. doi:10.1073/pnas.1006402107

[9]   M. J. Dai, B. Liang, C. Wang, Z. You, J. Xiang, G. Dong, J. Chen and Z. Yang, “A Novel Thiourea Ligand Applied in the Pd-Catalyzed Heck, Su-zuki and Suzuki Carbonylative Reactions,” Advanced Synthesis & Catalysis, Vol. 346, No. 13-15, 2004, pp. 1669-1673. doi:10.1002/adsc.200404165

[10]   W. Chen, R. Li, B. Han, B. J. Li, Y. C. Chen, Y. Wu, L. S. Ding and D. Yang, “The Design and Synthesis of Bis(thiourea) Ligands and Their Application in Pd-Catalyzed Heck and Suzuki Reactions under Aerobic Conditions,” European Journal of Organic Chemistry, Vol. 2006, No. 5, 2006, pp. 1177-1184. doi:10.1002/ejoc.200500644

[11]   Y. Lan, L. J. Deng, J. Liu, C. Wang, O. Wiest, Z. Yang and Y. D. Wu, “On the Mechanism of the Palladium Catalyzed Intramolecular Pauson-Khand-Type Reaction,” Journal of Organic Chemistry, Vol. 74, No. 14, 2009, pp. 5049-5058. doi:10.1021/jo900919v

[12]   B. Liang, J. Liu, Y. X. Gao, K. Wongkhan, D. X. Shu, Y. Lan, A. Li, A. S. Batsanov, J. A. H. Howard, T. B. Marder, J. H. Chen and Z. Yang, “Synthesis of Thiourea-Oxazolines, a New Class of Chiral S,N-Heterobidentate Ligands: Ap- plication in Pd-Catalyzed Asymmetric Bis(methoxycarbon-ylation) of Terminal Olefins,” Organometallics, Vol. 26, No. 19, 2007, pp. 4756-4762. doi:10.1021/om700311x

[13]   D. Cauzzi, M. Costa, N. Cucci, C. Graiff, F. Grandi, G. Predieri, A. Tiripicchio and R. Zanoni, “Pd(II) and Rh(I) Chelate Complexes of the Bidentate Phos-phino-Thiourea Ligand PhNHC(S)NHCH2CH2PPh2: Structural Properties and Activity in Homogeneous and Hybrid Catalysis,” Journal of Organometallic Chemistry, Vol. 593-594, No. 1, 2000, pp. 431-444. doi:10.1016/S0022-328X(99)00615-4

[14]   R. Abdallah, J. A. J. Breuzard, M. C. Bonnet and M. Le-maire, “Phosphite and Thiourea Ligand Synergy for Rho-dium Catalyzed Enantiose-lective Hydroformylation of Styrene,” Journal of Molecular Catalysis A: Chemical, Vol. 249, No. 1-2, 2006, pp. 218-222. doi:10.1016/j.molcata.2005.12.020

[15]   E. M. O. Yeboah, S. O. Yeboah and G. S. Singh, “Recent Applications of Cinchona Alkaloids and their Derivatives as Catalysts in Metal-free Asymmetric Synthesis,” Tetrahedron, Vol. 67, No. 10, 2011, pp. 1725-1762. doi:10.1016/j.tet.2010.12.050

[16]   T. Zhang, L. Cheng, S. Hameed, L. Liu, D. Wang and Y. J. Chen, “Highly Enantiose-lective Michael Addition of 2-Oxindoles to Vinyl Selenone in RTILs Catalyzed by a Cinchona Alkaloid-Based Thiourea,” Chemical Communi- cations, Vol. 47, No. 23, 2011, pp. 6644-6646. doi:10.1039/c1cc10880h

[17]   M. M. S. Duque, O. Baslé, N. Isambert, A. Gaudel-Siri, Y. Génisson, J. C. Plaquevent, J. Ro-driguez and T. Constantieux, “A Cooperative Participation of the Amido Group in the Organocatalytic Construction of All-Carbon Quaternary Stereocenters by Michael Addition with β-Ke- toamides,” Organic Letters, Vol. 13, No. 13, 2011, pp. 3296-3299. doi:10.1021/ol200924e

[18]   C. Kanta De and D. Seidel, “Catalytic Enantioselective Desymmetrization of me-so-Diamines: A Dual Small-Mo- lecule Catalysis Approach,” Journal of the American Chemical Society, Vol. 133, No. 37, 2011, pp. 14538-14541. doi:10.1021/ja2060462

[19]   A. E. Nowak, E. Wojaczyńska and J. Skar?ewski, “Enantiopure trans-1-Amino-2-(arylsulfanyl)cyclohexanes: Novel Chiral Motifs for Ligands and Organocatalysts,” Tetrahedron: Asymmetry, Vol. 22, No. 16-17, 2011, pp. 1687-1691. doi:10.1016/j.tetasy.2011.09.015

[20]   J. Wang, H. Li, X. H. Yu, L. S. Zu and W. Wang, “Chiral Binaphthyl-Derived Amine-Thiourea Organocatalyst-Promoted Asymmetric Mori-ta-Baylis-Hillman Reaction,” Organic Letters, Vol. 7, No. 19, 2005, pp. 4293-4296. doi:10.1021/ol051822+

[21]   M. Shi and X. G. Liu, “Asymme-tric Morita-Baylis-Hill- man Reaction of Arylaldehydes with 2-Cyclohexen-1-one Catalyzed by Chiral Bis(Thio)urea and DABCO,” Organic Letters, Vol. 10, No. 6, 2008, pp. 1043-1046. doi:10.1021/ol7028806

[22]   K. Liu, H. F. Cui, J. Nie, K. Y. Dong, X. J. Li and J. A. Ma, “Highly Enantioselective Michael Addition of Aro- matic Ketones to Nitroolefins Promoted by Chiral Bifunctional Primary Amine-Thiourea Catalysts Based on Saccharides,” Organic Letters, Vol. 9, No. 5, 2007, pp. 923-925. doi:10.1021/ol0701666

[23]   P. Gao, C. G. Wang, Y. Wu, Z. H. Zhou and C. C. Tang “Sugar-Derived Bifunctional Thiourea Organocatalyzed Asymmetric Michael Addition of Acetylacetone to Nitroolefins,” European Journal of Organic Chemistry, Vol. 2008, No. 27, 2008, pp. 4563-4566. doi:10.1002/ejoc.200800555

[24]   S. V. Pansare and E. K. Paul, “Organocatalytic Asymmet- ric Direct Vinylogous Aldol Reactions of γ-Crotonolactone with Aromatic Aldehydes,” Chemical Communications, Vol. 47, No. 3, 2011, pp. 1027-1029. doi:10.1039/c0cc04191b

[25]   P J. Y. Fu, Q. C Huang, Q. W. Wang, L. X. Wang and X. Y. Xu, “Highly Effective and Enan-tioselective α-Amination of Aldehydes Promoted by Chiral Proline Amide-Thiourea Bifunctional Catalysts,” Tetrahedron Letters, Vol. 51, No. 37, 2010, pp. 4870-4873. doi:10.1016/j.tetlet.2010.07.042

[26]   C. L. Cao, M. C. Ye, X. L. Sun and Y. Tang, “Pyr- rolidine-Thiourea as a Bifunctional Organocatalyst: Highly Enantioselective Michael Addition of Cyclohexanone to Nitroolefins,” Organic Letters, Vol. 8, No. 14, 2006, pp. 2901-2904. doi:10.1021/ol060481c

[27]   P. A. Wang, Z. S; Xu, C. F. Chen, X. G. Gao, X. L. Sun and S. Y. Zhang, “Facile Synthetic Route to Enantiopure Unsymmetric cis-2,5-Disubstituted Pyrrolidines,” Chirality, Vol. 19, No. 7, 2007, pp. 581-588. doi:10.1002/chir.20424

[28]   P. A. Wang, W. He, S. K. Chen and S. Y. Zhang, “Efficient Synthesis of Unnatural Dipeptides Based on cis-2,5- Disubstituted Pyrrolidine,” Amino Acids, in press, 2011, doi:10.1007/s00726-011-0949-4

[29]   E. J. Corey, H. Cho, C. Rcker and D. H. Hua, “Studies with Trialkylsilyl-triflates: New Syntheses and Applications,” Tetrahedron Letters, 1981, Vol. 22, No. 36, pp. 3455-3458. doi:10.1016/S0040-4039(01)81930-4