RING EXPANSION OF CYCLIC-OLEFINS BY OLEFIN METATHESIS REACTIONS WITH AN ACYCLIC DIENE

摘要

This invention relates generally to synthetic procedures that include the step of ring­opening metathesis of cyclic olefins and reaction with an acyclic diene co-reactant to produce olefin macrocycles by ring expansion, or alternatively, to produce regularly repeating A,B-alternating olefin polymers. The ring expansion of the cyclic olefin is provided by three types of sequential olefin metathesis (ring-opening, cross, and ring-closing olefin metathesis), and the A,B-alternating polymers are produced by simply varying the reaction conditions and/or reactant proportions and using only two types of olefin metathesis (ring-opening and cross) to provide regularly repeating ABAB...etc. polymers via ring-opening metathesis polymerization (ROMP). More particularly, the invention pertains to synthesis of olefin macrocycles and A,B-alternating olefin polymers via olefin metathesis reactions using a Group 8 transition metal complex as the metathesis catalyst. Macrocycles provided herein have a variety of uses in the pharmaceutical, biomedical, organic synthesis and chemical industries, such as the production of crown ethers that are useful as metal complexing species. Also, the polymers provided herein have utility in a variety of fields, including not only polymer chemistry per se, but also in the pharmaceutical, biomedical, and packaging industries where the structure and properties of polymers need to be tightly controlled.