The present disclosure provides methods for enantioselective synthesis of cyclic and acyclic -quaternary carboxylic acid derivatives via nickel-catalyzed allylic alkylation.

The present disclosure provides methods for enantioselective synthesis of cyclic and acyclic -quaternary carboxylic acid derivatives via nickel-catalyzed allylic alkylation.

The present disclosure provides methods for enantioselective synthesis of cyclic and acyclic -quaternary carboxylic acid derivatives via nickel-catalyzed allylic alkylation.

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.

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, X is an anionic ligand. A process for the preparation of the complex, and its use in carbon-carbon or carbon-nitrogen coupling reactions is also provided.

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.

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.