This invention relates generally to the synthesis of E-macrocycles using stereoretentive ruthenium olefin metathesis catalysts supported by dithioiate ligands. Macrocycles were generated with excellent selectivity (>99% E) and in moderate to high/good yields (47% to 80% yield; 58% to 80% yield) from diene starting materials bearing two E-olefins or bearing one E-olefin and one terminal olefin, A variety of rings were constructed, ranging from 12- to 18-membered macrocycles, including the antibiotic recifeiolide. The invention has utility in the fields of organometallics and organic synthesis.

[Problem] To provide a novel artificial protein catalyst that enables the protection of a catalyst from substances in vivo and has potential usefulness in therapeutic in vivo synthetic chemistry.

[Solution] Provided is a complex of a protein and a catalyst selected from a metal catalyst or organic catalyst. In the complex according to the present invention, the protein is a protein having a hydrophobic pocket in the three-dimensional structure thereof, and the catalyst is housed in the hydrophobic pocket so that the catalyst is not or substantially not exposed to a hydrophilic environment.

Embodiments in accordance with the present invention encompass compositions encompassing a latent organo-ruthenium compound, a photosensitizer and one or more monomers which undergo ring open metathesis polymerization (ROMP) when said composition is exposed to suitable actinic radiation to form a substantially transparent film or a three dimensional object. Surprisingly, the compositions are very stable at ambient conditions to temperatures up to 80° C. for several weeks and undergo mass polymerization only when subjected to actinic radiation under inert atmosphere such as for example a blanket of nitrogen. Accordingly, compositions of this invention are useful in various opto-electronic applications, including as 3D printing materials, coatings, encapsulants, fillers, leveling agents, among others.

The present disclosure provides compositions and methods for metathesizing a first alkenyl or alkynyl group with a second alkenyl or alkynyl group, the composition comprising a ruthenium metathesis catalyst and a photoredox catalyst that is activated by visible light.

Embodiments in accordance with the present invention encompass an organoruthenium compound of the formula (I) or formula (II):

##STR00001##

Wherein X, L, R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, Ar.sub.1 and Ar.sub.2 are as defined herein. Also disclosed herein are the use of organoruthenium compound of formula (I) or formula (II) as (pre)catalysts for the olefin metathesis reactions, as well as to the process for carrying out the olefin metathesis reaction.

In a ruthenium complex compound according to the present invention, an NHC ligand has an excellent electron-donating ability to stabilize methylidene species due to the steric interaction between substituents having relatively different sizes. The ruthenium complex compound can improve selectivity when used as a catalyst due to having an asymmetric structure, and the activity of the ruthenium complex compound can be improved by adjusting substituents and additives. Accordingly, the ruthenium complex compound can be used as a catalyst in cross metathesis reactions including ethenolysis to produce desired compounds such as linear α-olefins at high yield, even under relatively mild conditions.

The present invention relates to ligands based on calixarenes, metal complexes comprising such ligands and their use as homogeneous or heterogeneous catalysts.

Embodiments in accordance with the present invention encompass an organoruthenium compound of the formula (I) or formula (II): ##STR00001##
Wherein X, L, R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, Ar.sub.1 and Ar.sub.2 are as defined herein. Also disclosed herein are the use of organoruthenium compound of the formula (I) or formula (II) as (pre)catalysts for the olefin metathesis reactions, as well as to the process for carrying out the olefin metathesis reaction.

Provided herein are transition metal complexes that are useful in the acceptorless dehydrogenation of various substrates, including alkanes. Also provided are methods of dehydrogenating substrates to provide unsaturated products such as olefins.

The invention provides a new process for producing ruthenium complexes represented by the Formula 1. Invention provides also the use of ruthenium complexes represented by the Formula 1 as precatalysts and/or catalysts in olefin metathesis reactions.