Intermolecular Markovnikov-Selective Hydroacylation of Olefins Catalyzed by a Cationic Ruthenium–Hydride Complex

Asymmetric Rh-catalyzed intermolecular hydroacylation of 1,5-hexadiene with salicylaldehyde.

Asymmetric intermolecular hydroacylation between salicylaldehyde (1) and 1,5-hexadiene (2) using a combination of [RhCl(C(8)H(14))(2)](2) (0.10 eq), (S)-BINAP (0.10 eq), and ZnBr(2) (0.20 eq) afforded an enantiomerically enriched hydroacylated product iso-3 of 84% ee, along with an achiral product normal-3.

Gold(I)-catalyzed intra- and intermolecular hydroamination of unactivated olefins.

Ph3PAuOTf catalyzes efficient intra- and intermolecular hydroamination of unactivated olefins with sulfonamides.

Radical-mediated anti-Markovnikov hydrophosphonation of olefins.

The radical-mediated addition of triphenylphosphonium tetrafluoroborate to olefins (hydrophosphonation) is reported. Both standard radical initiators and photochemical conditions are effective, up to the gram scale. The phosphonium salts are shown to serve as Z-selective Wittig olefination reagents, even without purification.

Formal Anti-Markovnikov Hydroamination of Terminal Olefins.

A new strategy to access linear amines from terminal olefin precursors is reported. This two-step, one-pot hydroamination methodology employs sequential oxidation and reduction catalytic cycles. The formal hydroamination transformation proceeds with excellent regioselectivity, and only the anti-Markovnikov product is observed. Up to 70% yield can be obtained from styrenes or aliphatic olefins a...

Palladium-catalyzed selective anti-Markovnikov oxidation of allylic esters.