Unusual Water-Soluble Imino Phosphine Ligand: Enamine and Imine Derivatives of 1,3,5-Triaza-7-phosphaadamantane (PTA).

A series of water-soluble and air-stable E-enamine derivatives of 1,3,5-triaza-7-phosphaadamantane (PTA), PTA═C(R)NH, 1-4, are reported along with data on E-Z isomerization and tautomerization to the imine form (PTA-CR═NH). Reaction of 1,3,5-triaza-7-phosphaamantane-6-yl lithium, PTA-Li, with aromatic nitriles afforded E-enamine derivatives of PTA in good yield (49-91%). Phosphines 1-4 are stable toward water and air, and do not appear to isomerize or tautomerize, unless coordinated to a metal or oxidized.

Nickel-catalysed para-CH activation of pyridine with switchable regioselective hydroheteroarylation of allylarenes.

para-CH activation of pyridine with allylbenzene is described by Ni/Al cooperative catalysis in combination with a bulkier NHC ligand and a Lewis acid, leading to linear hydroheteroarylation products. Interestingly, the branch selectivity can be achieved by using the combination of a less sterically hindered amino-NHC ligand and AlMe3 through tandem reaction of facile alkene isomerization followed by a slow CH bond activation process.

Controlled regiodivergent C-H bond activation of imidazo[1,5-a]pyridine via synergistic cooperation between aluminum and nickel.

The catalytic method features a cooperative interaction between Ni and Al imparting remote C-H alkenylation at the C5 position of imidazo[1,5-a]pyridine with alkynes at mild conditions. Exclusion of AlMe3 switches the selectivity to the C3 position. Reactions with styrene and other olefinic substrates affording C5-adducts by Ni/Al catalysis are also included.

Ligand promoted Pd-catalyzed dehydrogenative alkenylation of hetereoarenes.

An efficient Pd-catalyzed cross-dehydrogenative coupling of heteroarenes with styrenes and other olefinic substrates has been developed. This alkenylation paradigm encompasses a wide range of substrates and provides a straightforward approach toward C2-E-alkenylated azole motifs.

Tandem isomerization and C-H activation: regioselective hydroheteroarylation of allylarenes.

The first Ni-promoted prototype reaction based on the tandem C-H activation of heteroarenes with alkene isomerization is demonstrated, leading to the branched hydroheteroarylation products. Simultaneously, the reaction selectivity can be chemically switched to linear adducts through Ni-Al tandem catalysis.

Hemilabile β-aminophosphine ligands derived from 1,3,5-triaza-7-phosphaadamantane: application in aqueous ruthenium catalyzed nitrile hydration.

A series of β-aminophosphines derived from 1,3,5-triaza-7-phosphaadamantane (PTA) are described. PTA-CHPhNHPh (1), PTA-CH(p-C(6)H(4)OCH(3))NHPh (2), and PTA-CPh(2)NHPh (3) were prepared in good yield (62-77%) by reaction of lithiated PTA with the corresponding imine followed by hydrolysis. Compounds 1 and 2 were synthesized as pairs of diastereomers which were separated by successive recrystallization from THF/hexane.

Insertion of CO2, ketones, and aldehydes into the C-Li bond of 1,3,5-triaza-7-phosphaadamantan-6-yllithium.

The synthesis and structures of a series of new water-soluble phosphine ligands based on 1,3,5-triaza-7-phosphaadamantane (PTA) are described. Insertion of aldehydes or ketones into the C-Li bond of 1,3,5-triaza-7-phosphaadamantan-6-yllithium (PTA-Li) resulted in the formation of a series of slightly water-soluble beta-phosphino alcohols (PTA-CRR'OH, R = C6H5, C(6)H(4)OCH(3), ferrocenyl; R' = H, C(6)H(5), C(6)H(4)OCH(3)) derived from the heterocyclic phosphine PTA. Insertion of CO(2) yielded the highly water-soluble carboxylate PTA-CO(2)Li, S(2)5 degrees approximately 800 g/L.