Zirconium-catalyzed intermolecular hydrophosphination using a chiral, air-stable primary phosphine.

Catalytic hydrophosphination of alkenes using a chiral, air-stable primary phosphine, (R)-[2'-methoxy(1,1'-binapthalen)-2-yl]phosphine, (R)-MeO-MOPH2, proceeds under mild conditions with a zirconium catalyst, [κ(5)-N,N,N,N,C-(Me3SiNCH2CH2)2NCH2CH2NSiMe2CH]Zr (1), to selectively furnish anti-Markovnikov, air-stable secondary phosphines or tertiary phosphines with slight modification of the protocol. An intermediate in the catalysis, [(N3N)Zr(R)-MeO-MOPH] (4), was structurally characterized.

Intermolecular zirconium-catalyzed hydrophosphination of alkenes and dienes with primary phosphines.

Catalytic hydrophosphination of terminal alkenes and dienes with primary phosphines (RPH2; R = Cy, Ph) under mild conditions has been demonstrated using a zirconium complex, [κ(5)-N,N,N,N,C-(Me3SiNCH2CH2)2NCH2CH2NSiMe2CH]Zr (1). Exclusively anti-Markovnikov functionalized products were observed, and the catalysis is selective for either the secondary or tertiary phosphine (i.e., double hydrophosphination) products, depending on reaction conditions. The utility of the secondary phosphine products as substrates for further elaboration was demonstrated with a platinum-catalyzed asymmetric alkylation reaction.

Differences in the stability of zirconium(IV) complexes related to catalytic phosphine dehydrocoupling reactions.

Relating to the catalytic dehydrocoupling of secondary phosphine substrates, zirconium phosphide complexes supported by triamidoamine and pentamethylcyclopentadienyl ligands exhibit different stability that is attributed to ß-hydride elimination.