Synthesis, Characterization, Polymerization of Optically Active Terminal Epoxides and Episulfides Bearing Bulky Groups

doi:10.1007/s40242-013-2299-0

Chemical Research in Chinese Universities ›› 2013, Vol. 29 ›› Issue (2): 239-244.doi: 10.1007/s40242-013-2299-0

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Synthesis, Characterization, Polymerization of Optically Active Terminal Epoxides and Episulfides Bearing Bulky Groups

SUN Yun-kai^1,2, ZHANG Jin¹, LIU Hui-jun², HE Li¹, GONG Hang¹, YANG Nian-fa¹

1. Key Laboratory of Environmentally Friendly Chemistry and Applications of Ministry of Education, College of Chemistry, Xiangtan University, Xiangtan 411105, P. R. China;
2. School of Chemistry and Chemical Engineering, University of South China, Hengyang 421001, P. R. China

Received:2012-08-13 Revised:2012-09-06 Online:2013-04-01 Published:2013-03-20
Supported by:
Supported by the National Natural Science Foundation of China(No.20972131), the Research Foundation for Doctors, University of South China(No.2011XQD55) and the Natural Science Foundation of Xiangtan University, China(No.10XZX08).

Abstract

Abstract:

A simple and efficient protocol was developed for the syntheses of optically active epoxides(2a-2d) via the reactions of epichlorohydrin with organometallic reagents with steric hindrance at low temperature. On this basis, episulfides(3a-3d) were obtained with high e.e. values by the reaction of the corresponding epoxides with NH₄SCN. The configuration of thiiranes was opposite to that of the corresponding epoxides. Then, epoxides 2a-2d were anionically polymerized and the poly-R-2a(or poly-S-2a) was proved to keep a stable one-handed helical conformation in solution. The oligomers[degree of polymerization(DP)=2-5] were obtained when the thiiranes(3a, 3b and 3c) were used to polymerize.

Key words: Optical activity, Epoxide, Episulfide, One-handed helicity

SUN Yun-kai, ZHANG Jin, LIU Hui-jun, HE Li, GONG Hang, YANG Nian-fa. Synthesis, Characterization, Polymerization of Optically Active Terminal Epoxides and Episulfides Bearing Bulky Groups[J]. Chemical Research in Chinese Universities, 2013, 29(2): 239-244.

References

[1] Shi Y. A., Acc. Chem. Res., 2004, 37, 488

[2] Fan Q. H., Li Y. M., Chan A. S. C., Chem. Rev., 2002, 102, 3385

[3] Zhao M. X., Shi Y. A., J. Org. Chem., 2006, 71, 5377

[4] Das B., Reddy V. S., Krishnaiah M., Tetrahedron Lett., 2006, 47, 8471

[5] Yadav J. S., Reddy B. V. S., Baishya G., Synlett., 2003, 396

[6] Sarma K., Bhati N., Borthakur N., Goswami A., Tetrahedron, 2007, 63, 8735

[7] Sun Y. K., Yang N. F., Wu S., Ling Y., Ouyang K. B., Chem. J. Chinese Universities, 2009, 30(8), 1559

[8] Spassky N., Sigwalt P., Tetrahedron Lett., 1968, 9, 3541

[9] Quirk R. P., Ocampo M., Polce M. J., Wesdemiotis C., Macromolecules, 2007, 40, 2352

[10] Vedejs E., Krafft G. A., Tetrahedron, 1982, 38, 2857

[11] Kleiner C. M., Horst L., Würtele C., Wende R. Schreiner P. R., Org. Biomol. Chem., 2009, 7, 1397

[12] Cao J., Yang N. F., Wang P. D., Yang, L. W., Polym. Int., 2008, 57, 530

[13] Cao J., Yang N. F., Li J. C., Yang L. W., Polym. Bull., 2007, 59, 481

[14] Sun Y. K., Yang N. F., Liu J., Cao J., Gong H., Polymer, 2010, 51, 5712

[15] Yadav J. S., Reddy B. V. S., Reddy C. S., Reddy C. S., Rajasekhar K., J. Org. Chem., 2003, 68, 2525

[16] Sander M., Chem. Rev., 1966, 66, 297

[17] Aghapour G., Hatefipour R., Synthetic Communications, 2009, 39, 1698

[18] Kurt L. S., Becker E. I., Org. Synth., 1963, 4, 623

[19] Thibblin A., Sidhu H., J. Am. Chem. Soc., 1992, 114, 7403

[20] Yuan T. M., Luh T. Y., Org. Synth., 1998, 9, 649

[21] Hodgson D. M., Salik S., Fox D. J., J. Org. Chem. 2010, 75, 2157

[22] Zhou C., Xu J. X., Prog. Chem., 2011, 23, 165

[23] Kavala M., Mathia F., Ko?íšek J., Szolcsányi P., J. Nat. Prod., 2011, 74, 803

[24] Kubizna P., Špánik I., Ko?íšek J., Szolcsányi P., Tetrahedron, 2010, 66, 2351

[25] Holub N., Neidhöfer J., Blecher S., Org. Lett., 2005, 7, 1227

[26] Price C. C., Kirk P. F., J. Am. Chem. Soc., 1953, 75, 2396

[27] Cao H. Q., Cui J. X., Liu A. H, Wan X. H., Acta Polym. Sin., 2010, 2, 222

[28] Yashima E., Maeda K., Iida H., Furusho Y., Nagai K., Chem. Rev., 2009, 109, 6102

Synthesis, Characterization, Polymerization of Optically Active Terminal Epoxides and Episulfides Bearing Bulky Groups

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