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

doi:10.1007/s40242-013-2299-0

高等学校化学研究 ›› 2013, Vol. 29 ›› Issue (2): 239-244.doi: 10.1007/s40242-013-2299-0

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

收稿日期:2012-08-13 修回日期:2012-09-06 出版日期:2013-04-01 发布日期:2013-03-20
通讯作者: YANG Nian-fa E-mail:nfyang@xtu.edu.cn
基金资助:
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).

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).

摘要/Abstract

摘要：

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.

关键词: Optical activity, Epoxide, Episulfide, One-handed helicity

Abstract:

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]. 高等学校化学研究, 2013, 29(2): 239-244.

参考文献

[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

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

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 4

编辑推荐

Metrics

本文评价

[1]	WANG Wenyang, LIU Hanlin, YANG Caoyu, FAN Ting, CUI Chengqian, LU Xiaoquan, TANG Zhiyong, LI Guodong. Coordinating Zirconium Nodes in Metal-Organic Framework with Trifluoroacetic Acid for Enhanced Lewis Acid Catalysis[J]. 高等学校化学研究, 2022, 38(5): 1301-1307.
[2]	SUN Huayan, QIN Jiaming, LI Yi, LI Baozong, YANG Yonggang. Characterization of a Chiral Low Molecular Weight Gelator in Gel State Using Various Circular Dichroism Methods[J]. 高等学校化学研究, 2017, 33(1): 119-121.
[3]	CAO Jun-gang, CAO Hui-min, LIN Ying-jie, LIANG Da-peng, DUAN Hai-feng*, HAN Song. Lewis Acidic Guanidinium Ionic Liquids: Novel, Efficient and Recyclable Catalysts for Aminolysis of Epoxides[J]. 高等学校化学研究, 2011, 27(5): 780-783.
[4]	HUANG Ru-dan, LI Juan, ZHANG Jing. Synthesis, Characterization and Conductivity of α-Keggin-type Nanoparticles, Co(en)<sub>3</sub>PMo<sub>12</sub>O<sub>40</sub>·8H<sub>2</sub>O with Optical Activity[J]. 高等学校化学研究, 2005, 21(1): 1-3.