Synthesis of terminal alkenes from internal alkenes and ethylene via olefin metathesis

摘要

This invention relates generally to olefin metathesis, and more particularly relates to the synthesis of terminal alkenes from internal alkenes using a cross-metathesis reaction catalyzed by a selected olefin metathesis catalyst. In one embodiment of the invention, for example, a method is provided for synthesizing a terminal olefin, the method comprising contacting an olefinic substrate comprised of at least one internal olefin with ethylene, in the presence of a metathesis catalyst, wherein the catalyst is present in an amount that is less than about 1000 ppm relative to the olefinic substrate, and wherein the metathesis catalyst has the structure of formula (II);
wherein the various substituents are as defined herein. The invention has utility, for example, in the fields of catalysis, organic synthesis, and industrial chemistry.

主权项

1. A method for synthesizing a metathesis reaction product having a terminal olefin, the method comprising contacting, in the presence of a metathesis catalyst, an olefinic substrate comprised of at least one internal olefin with ethylene, wherein the catalyst is present in an amount that is less than about 1000 ppm relative to the amount of the olefinic substrate, and wherein the metathesis catalyst has the structure of formula (XII): wherein: M is Ru or Os; t is zero; X1 and X2 are anionic ligands; R1 and R2 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, and substituted heteroatom-containing hydrocarbyl; Z3 is a cationic moiety selected from the group consisting of P(R2)3 and N(R2)3; Y is a non-coordinating anion; and L1 is a carbene ligand with the structure of formula (IIIc): wherein Ar1 and Ar2 are independently aryl substituted with at least one group selected from the group consisting of C1-C12 alkyl, C2-C12 alkenyl, C2-C12 alkynyl, C5-C12 aryl, C6-C12 aralkyl, and C6-C12 alkaryl; a is an optional double bond; R13, R14, R15, and R16 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, and substituted heteroatom-containing hydrocarbyl, wherein any two or more of A1, Ar2, R13, R14, R15, and R16 may be taken together to form a cyclic group, and provided that R14 and R16 are not present if a is present.