In one aspect, phosphine compounds comprising three adamantyl moieties (PAd.sub.3) and associated synthetic routes are described herein. Each adamantyl moiety may be the same or different. For example, each adamantyl moiety (Ad) attached to the phosphorus atom can be independently selected from the group consisting of adamantane, diamantane, triamantane and derivatives thereof. Transition metal complexes comprising PAd.sub.3 ligands are also provided for catalytic synthesis including catalytic cross-coupling reactions.

In one aspect, phosphine compounds comprising three adamantyl moieties (PAd.sub.3) and associated synthetic routes are described herein. Each adamantyl moiety may be the same or different. For example, each adamantyl moiety (Ad) attached to the phosphorus atom can be independently selected from the group consisting of adamantane, diamantane, triamantane and derivatives thereof. Transition metal complexes comprising PAd.sub.3 ligands are also provided for catalytic synthesis including catalytic cross-coupling reactions.

Disclosed are complexes and methods of using the complexes as catalysts for addition of amines to unsaturated electrophiles, as well as novel compounds produced by the disclosed complexes and methods. The disclosed methods may utilize the disclosed complexes as catalysts for adding unprotected primary amines and secondary amines to unsaturated electrophiles in an enantioselective manner to produce novel compounds which may include amino substituted succinimide compounds.

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.

The present disclosure relates to bis(aryl phenolate) Lewis base catalysts. Catalysts, catalyst systems, and processes of the present disclosure can provide high temperature ethylene polymerization, propylene polymerization, or copolymerization as the bis(aryl phenolate) Lewis base catalysts are stable at high polymerization temperatures and have good activity at the high polymerization temperatures. The stable catalysts with good activity can provide formation of polymers having high molecular weights and the ability to make an increased amount of polymer in a given reactor, as compared to conventional catalysts. Hence, the present disclosure demonstrates highly active catalysts capable of operating at high reactor temperatures while producing polymers with controlled molecular weights and or robust isotacticity.

This invention relates to transition metal complexes of a dianionic, tridentate ligand that features a central neutral heterocyclic Lewis base and two phenolate donors, where the tridentate ligand coordinates to the metal center to form two eight-membered rings. Preferably the bis(phenolate) complexes are represented by Formula (I):

##STR00001##

where M, L, X, m, n, E, E, Q, R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.1, R.sup.2, R.sup.3, R.sup.4, A.sup.1, A.sup.1,

##STR00002##

are as defined herein, where A.sup.1QA.sup.1 are part of a heterocyclic Lewis base containing 4 to 40 non-hydrogen atoms that links A.sup.2 to A.sup.2 via a 3-atom bridge with Q being the central atom of the 3-atom bridge.

This invention relates to supported catalyst compositions of transition metal complexes of a dianionic, tridentate ligand that features a central neutral heterocyclic Lewis base and two phenolate donors, where the tridentate ligand coordinates to the metal center to form two eight-membered rings. Preferably the bis(phenolate) complexes are represented by Formula (I):

##STR00001##

where M, L, X, m, n, E, E, Q, R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.1, R.sup.2, R.sup.3, R.sup.4, A.sup.1, A.sup.1, A.sup.3A.sup.2, and A.sup.2A.sup.3 are as defined herein, where A.sup.1QA.sup.1 are part of a heterocyclic Lewis base containing 4 to 40 non-hydrogen atoms that links A.sup.2 to A.sup.2 via a 3-atom bridge with Q being the central atom of the 3-atom bridge.

The present invention provides a complex of formula (1), ##STR00001##
wherein, M is palladium or nickel, R.sub.1 and R.sub.2 are independently organic groups having 1-20 carbon atoms, or R.sub.1 and R.sub.2 are linked to form a ring structure with the phosphorus atom, R.sub.3 is selected from the group consisting of substituted and unsubstituted aryl, substituted and unsubstituted heteroaryl, and substituted and unsubstituted metallocenyl, R.sub.4 is an organic group having 1-20 carbon atoms, n is 0, 1, 2, 3, 4 or 5, and X is an anionic ligand. The invention also provides a process for the preparation of the complex, and its use in carbon-carbon or carbon-nitrogen coupling reactions.

Disclosed are complexes and methods of using the complexes as catalysts for addition of amines to unsaturated electrophiles, as well as novel compounds produced by the disclosed complexes and methods. The disclosed methods may utilize the disclosed complexes as catalysts for adding unprotected primary amines and secondary amines to unsaturated electrophiles in an enantioselective manner to produce novel compounds which may include amino substituted succinimide compounds.

The subject invention pertains to a method of halogenating phenols, yielding a range of halogenated phenols with enantiomeric ratio of up to 99.5:0.5. In certain embodiments, the subject invention pertains to a method of asymmetric halogenation of bisphenol, yielding a range of chiral bisphenol ligands. The novel chiral bisphenols are potent privileged catalyst cores that can be applied to the preparation of ligands for various catalytic asymmetric reactions. The catalyst library can easily be accessed because late-stage modification of the scaffold can readily be executed through cross-coupling of the halogen handles on the bisphenols.