This article is part of the 2014 Small Heterocycles in Synthesis special issue. Ian Childers (second from right) was born in Latrobe, PA, in 1987. He received his B.S. degree in Chemistry from Washington and Lee University in 2010, where he performed research under the guidance of Erich Uffelman. He is currently a Ph.D. student at Cornell University in the group of Geoff Coates, where his research interests include bimetallic catalysis and epoxide polymerization. Julie Longo (left) was born in Atlanta, GA. She attended Emory University and received her B.S. degree in Chemistry in 2011. She entered the Ph.D. program at Cornell University in 2011 and joined the lab of Geoff Coates, where she is currently a National Science Foundation Graduate Research Fellow. Her research interests include developing biodegradable polymers from cyclic anhydrides and epoxides. Nathan Van Zee (second from left) grew up in Lake Worth, FL, and graduated from the Harriet L. Wilkes Honor College of Florida Atlantic University in 2010 with a B.A. degree in Liberal Arts with a concentration in chemistry. He is currently a Ph.D. student at Cornell University in the group of Geoff Coates, where he is an NSF IGERT Fellow. His research interests include catalysis and polyester synthesis. Anne LaPointe (middle) grew up in Sunnyvale, CA, and received her B.S. degree in Chemistry from Stanford University in 1990 and Ph.D. degree in Inorganic Chemistry from the Massachusetts Institute of Technology in 1994 with Professor Richard R. Schrock. She then moved to the University of North Carolina at Chapel Hill, where she was a NSF Postdoctoral Fellow in Professor Maurice S. Brookhart’s group. In 1997 she returned to California and joined Symyx Technologies as a member of the catalysis group. She has been at Cornell University since 2010, where she is Director of the Catalyst Discovery and Development Laboratory. Her research interests include catalysis, high-throughput experimentation, synthetic inorganic and organometallic chemistry, and polymer chemistry. Geoff Coates (right) was born in 1966 in Evansville, IN. He received his B.A. degree in Chemistry from Wabash College in 1989 working with Roy G. Miller and Ph.D. degree in Organic Chemistry from Stanford University in 1994 with Robert M. Waymouth. After being an NSF Postdoctoral Fellow with Robert Grubbs at the California Institute of Technology, he joined the faculty at Cornell University in 1997 and was appointed to the first Tisch University Professorship in 2008. Research in the Coates group focuses on development of single-site catalysts for small molecule and polymer synthesis as well as preparation and characterization of well-defined polymer architectures. ^aOP = polymer chain. ^aOP = polymer chain. ^aL_n^★ is a chiral ligand set. ^aL_n^★ is a chiral ligand set. Figure 1. Classification of stereocontrol according to type of epoxide and catalyst (L^R_n and L^S_n are chiral ligand sets that give R- and S-preferring catalysts, respectively). Figure 2. Methine and methylene regions of the ¹³C NMR spectra of atactic and isotactic poly(propylene oxide). Figure 3. Depiction of a proposed [(RO)₄Al₂O₂Zn]₈ aggregate ((RO)₄Al₂O linkages are truncated for clarity). Figure 4. Well-defined complexes for polymerization of epoxides (dmca = dimethylcalixarene; salcy = N,N′-bis-(2-hydroxybenzylidene)-(1R,2R)-cyclohexane-1,2-diamine; tpp = 5,10,15,20-tetraphenylporphyrin). Figure 5. Structures of complexes 13 and 14. Figure 6. Structure of complex 15. Figure 7. X-ray crystal structure of 20. Figure 8. Bimetallic catalysts for epoxide polymerizations. Figure 9. Stereoselective polymerizations with (a) meso-epoxides and (b) terminal rac-epoxides. ^an.d. = not determined, DNP = 2,4-dinitrophenoxide, PPN = bis(triphenylphosphine)iminium, MTBD = 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, DMAQ = N,N-4-dimethylaminoquinoline. ^an.d. = not determined, DNP = 2,4-dinitrophenoxide, PPN = bis(triphenylphosphine)iminium, MTBD = 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, DMAQ = N,N-4-dimethylaminoquinoline. Figure 10. Structures of complexes 40 and 31f. Figure 11. Structures of complexes 45–48. The authors declare no competing financial interest. We thank the NSF (CHE-1136607 and CHE-1112278) for generous financial support of our work in the field of epoxide polymerization. J.M.L. thanks the NSF for a Graduate Research Fellowship, and N.J.V.Z. acknowledges support from the NSF IGERT program (DGE-0903653). This article references 116 other publications.

中文翻译：

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立体选择性环氧聚合和共聚

本文是 2014年合成中的小型杂环 特刊。 Ian Childers（右二）于1987年出生于宾夕法尼亚州的拉特罗布。他于2010年获得华盛顿和利大学的化学学士学位，并在Erich Uffelman的指导下进行了研究。他目前是一名博士学位。康奈尔大学Geoff Coates小组的学生，他的研究兴趣包括双金属催化和环氧化物聚合。朱莉·隆戈（Julie Longo）（左）出生于佐治亚州亚特兰大。她进入埃默里大学（Emory University）并于2011年获得化学学士学位。她于2011年在康奈尔大学（Cornell University）取得博士学位，并加入了Geoff Coates实验室，目前是美国国家科学基金会的研究生研究员。她的研究兴趣包括从环酐和环氧化物开发可生物降解的聚合物。内森·范·泽（Nathan Van Zee）（左二）在佛罗里达州沃思湖长大，并于2010年毕业于佛罗里达大西洋大学的Harriet L. Wilkes荣誉学院，并获得了化学专业的文科学士学位。他目前是一名博士学位。康奈尔大学Geoff Coates小组的学生，他是NSF IGERT研究员。他的研究兴趣包括催化和聚酯合成。Anne LaPointe（中）在加利福尼亚州森尼韦尔长大，并于1990年获得了斯坦福大学的化学学士学位和博士学位。1994年获得麻省理工学院无机化学博士学位，理查德·R·施罗克（Richard R. Schrock）教授。然后，她搬到北卡罗来纳大学教堂山分校，在那里她是莫里斯·布鲁克哈特教授的小组的NSF博士后研究员。1997年，她返回加利福尼亚，加入Symyx Technologies，担任催化小组成员。自2010年以来，她一直在康奈尔大学任职，是催化剂发现与开发实验室的主任。她的研究兴趣包括催化，高通量实验，合成无机和有机金属化学以及聚合物化学。杰夫·科茨（Geoff Coates）（右）于1966年出生于印第安纳州的埃文斯维尔。他于1989年在Wabash学院获得化学学士学位，并与Roy G. Miller和Ph.D.合作。1994年与Robert M. Waymouth获得斯坦福大学有机化学博士学位。在成为加州理工学院的Robert Grubbs的NSF博士后研究员之后，他于1997年加入康奈尔大学，并于2008年被任命为第一届Tisch大学教授。^一个OP =聚合物链。^一个OP =聚合物链。^一个大号_Ñ ^★是手性配体组。^一个大号_Ñ ^★是手性配体组。图1.根据环氧化物和催化剂的类型进行立体控制的分类（L ^R _n和L ^S _n是分别给出R-和S-优选催化剂的手性配体对）。图2.无规和等规聚环氧丙烷的¹³ C NMR光谱的蛋氨酸和亚甲基区域。图3.拟议的[（RO）₄ Al ₂ O ₂ Zn]的描述_8个骨料（（RO）₄ Al ₂ O的连接被截短以求清楚）。图4.定义明确的用于环氧化物聚合的络合物（dmca =二甲基杯芳烃； salcy = N，N'-双-（2-羟基苄叉基）-（1 R，2 R）-环己烷-1，2-二胺； tpp = 5 ，10,15,20-四苯基卟啉）。图5.配合物13和14的结构。图6.配合物的结构15。图7的X射线晶体结构20。图8.用于环氧化物聚合的双金属催化剂。图9.立体选择性聚合用的（a）内消旋环氧化物和（b）终端外消旋-环氧化物。^一个日期不详 =未测定，DNP = 2,4-二硝基苯酚盐，PPN =双（三苯基膦）亚铵，MTBD = 7-甲基-1,5,7-三氮杂双环[4.4.0]癸-5-烯，DMAQ = Ñ，ñ - 4-二甲基氨基喹啉。^一个日期不详 =未测定，DNP = 2,4-二硝基苯酚盐，PPN =双（三苯基膦）亚铵，MTBD = 7-甲基-1,5,7-三氮杂双环[4.4.0]癸-5-烯，DMAQ = Ñ，ñ - 4-二甲基氨基喹啉。图10.配合物40和31f的结构。图11.配合物的结构45 – 48。作者宣称没有竞争性的经济利益。感谢NSF（CHE-1136607和CHE-1112278）对我们在环氧化物聚合领域的工作提供的慷慨资助。JML感谢NSF提供的研究生研究奖学金，并且NJVZ感谢NSF IGERT计划（DGE-0903653）的支持。本文引用了其他116种出版物。