α-Olefins are the most abundant petrochemical feedstock beyond alkanes, yet their use in commodity chemical manufacture is largely focused on polymerization and hydroformylation. The development of byproduct-free catalytic C-C bond forming reactions that convert olefins to value-added products remains an important objective. Here, we review catalytic intermolecular reductive couplings of unactivated and activated olefin-derived nucleophiles with carbonyl partners. These processes represent an alternative to the longstanding use of stoichiometric organometallic reagents in carbonyl addition.

Using an iridium catalyst modified by PhanePhos, CF3-allenes react with methanol to form branched products of hydrohydroxymethylation as single regioisomers with excellent levels of enantiomeric enrichment. This hydrogen auto-transfer process enables catalytic enantioselective formation of acyclic CF3-bearing all-carbon quaternary stereocenters in the absence of stoichiometric metals or byproducts.

Alcohol is the Answer! Ruthenium(II) complexes catalyze the C-C coupling of 1,1-disubstituted allenes and fluorinated alcohols to form homoallylic alcohols bearing all-carbon quaternary centers with good to complete levels of diastereoselectivity. Whereas fluorinated alcohols are relatively abundant and tractable, the corresponding aldehydes are often not commercially available due to their instability.

The direct approach: Ruthenium(0)‐catalyzed hydrohydroxyalkylation of α‐olefins and styrenes with 3‐hydroxy‐2‐oxindoles forms branched products of CC coupling with high levels of diastereocontrol. A mechanism involving diene–olefin oxidative coupling and a subsequent carboxylic acid co‐catalyzed transfer hydrogenolysis of the resulting oxaruthenacycle intermediate is postulated.

A Pd-catalyzed reaction of vinyl iodides and N-tosylhydrazones that assembles η(3)-allyl ligands through carbene insertion is demonstrated. Intramolecular trapping with nitrogen nucleophiles generates good yields of cinnamyl and pentadienyl amines like those found in alkaloid natural products. Carbenylative amination was the key reaction to complete the synthesis of the alkaloid caulophyllumine B. Migratory insertion was biased to provide allylamines with optical purity up to 64% ee, but in a lower yield.