1-取代环丁烯的开环复分解聚合（ROMP）反应的范围。
Scope of the ring-opening metathesis polymerization (ROMP) reaction of 1-substituted cyclobutenes.
机构信息
Department of Chemistry, Stony Brook University, Stony Brook, New York 11794-3400, USA.
出版信息
J Am Chem Soc. 2010 Aug 4;132(30):10513-20. doi: 10.1021/ja1037098.
Abstract
The reactivities of a series of 1-substituted cyclobutene derivatives (carboxylate esters, carboxamides, and carbinol esters) were investigated as substrates for ring-opening metathesis polymerization (ROMP) with [(H(2)IMes)(3-Br-pyridine)(2)(Cl)(2)Ru=CHPh]. Both the secondary amides of 1-cyclobutenecarboxylic acid and the esters of 1-cyclobutene-1-methanol undergo polymerization. The secondary amides provide translationally invariant polymers (E-olefins). Although the carbinol esters yield stereo- and regiochemically heterogeneous polymers, the 1-cyclobutenecarboxylic acid esters and tertiary amides undergo ring-opening metathesis (ROM) but not ROMP. The regio- and stereochemical outcomes of these ROMP and ROM reactions were analyzed at the B3LYP/6-31G* and LANL2DZ levels of theory. Calculations suggest that the regiochemistry and stereochemistry of the addition to the propagating carbene to form the metallocyclobutane intermediate depend on both charge distribution and steric interactions.
摘要
研究了一系列 1-取代环丁烯衍生物（羧酸酯、酰胺和醇酯）作为[(H(2)IMes)(3-Br-吡啶)(2)(Cl)(2)Ru=CHPh]开环复分解聚合（ROMP）的底物的反应性。1-环丁烯羧酸的仲酰胺和 1-环丁烯-1-甲醇的酯都能进行聚合。仲酰胺提供平移不变的聚合物（E-烯烃）。尽管醇酯产生立体和区域化学异构的聚合物，但 1-环丁烯羧酸酯和叔酰胺经历开环复分解（ROM）而不是 ROMP。这些 ROMP 和 ROM 反应的区域和立体化学结果在 B3LYP/6-31G*和 LANL2DZ 理论水平上进行了分析。计算表明，形成金属环丁烷中间体的增长卡宾加成的区域化学和立体化学取决于电荷分布和空间相互作用。
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