Formate-Mediated Reductive Cross-Coupling of Vinyl Halides and Aryl Iodides: -Substitution via Palladium(I) Catalysis.

Formate-mediated reductive cross-couplings of vinyl halides with aryl iodides via palladium(I) catalysis occur with highly uncommon -substitution. The active dianionic palladium(I) catalyst, [PdI][NBu], is generated from Pd(OAc), BuNI, and formate. Oxidative addition of aryl iodide followed by dissociation of the dimer provides the monomeric anionic T-shaped arylpalladium(II) species, [Pd(Ar)(I)(NBu)], which, upon vinyl halide carbopalladation, forms products of -substitution by way of palladium(IV) carbenes, as corroborated by deuterium-labeling experiments.

Leveraging the Stereochemical Complexity of Octahedral Diastereomeric-at-Metal Catalysts to Unlock Regio-, Diastereo-, and Enantioselectivity in Alcohol-Mediated C-C Couplings via Hydrogen Transfer.

Experimental and computational studies illuminating the factors that guide metal-centered stereogenicity and, therefrom, selectivity in transfer hydrogenative carbonyl additions of alcohol proelectrophiles catalyzed by chiral-at-metal-and-ligand octahedral d metal ions, iridium(III) and ruthenium(II), are described. To augment or invert regio-, diastereo-, and enantioselectivity, predominantly one from among as many as 15 diastereomeric-at-metal complexes is required. For iridium(III) catalysts, cyclometalation assists in defining the metal stereocenter, and for ruthenium(II) catalysts, iodide counterions play a key role.

Carbonyl Allylation and Crotylation: Historical Perspective, Relevance to Polyketide Synthesis, and Evolution of Enantioselective Ruthenium-Catalyzed Hydrogen Auto-Transfer Processes.

The evolution of methods for carbonyl allylation and crotylation of alcohol proelectrophiles culminating in the design of iodide-bound ruthenium-JOSIPHOS catalysts is prefaced by a brief historical perspective on asymmetric carbonyl allylation and its relevance to polyketide construction. Using gaseous allene or butadiene as precursors to allyl- or crotylruthenium nucleophiles, respectively, new capabilities for carbonyl allylation and crotylation have been unlocked, including stereo- and site-selective methods for the allylation and crotylation of 1,3-diols and related polyols.

Chiral-at-Ruthenium-SEGPHOS Catalysts Display Diastereomer-Dependent Regioselectivity: Enantioselective Isoprene-Mediated Carbonyl -Prenylation via Halide Counterion Effects.

The first correlation between metal-centered stereogenicity and regioselectivity in a catalytic process is described. Alternate -diastereomeric chiral-at-ruthenium complexes of the type RuX(CO)[η-prenyl][()-SEGPHOS] form in a halide-dependent manner and display divergent regioselectivity in catalytic C-C couplings of isoprene to alcohol proelectrophiles via hydrogen autotransfer. Whereas the chloride-bound ruthenium-SEGPHOS complex prefers a -relationship between the halide and carbonyl ligands and delivers products of carbonyl -prenylation, the iodide-bound ruthenium-SEGPHOS complex prefers a -relationship between the halide and carbonyl ligands and delivers products of carbonyl -prenylation.

From Hydrogenation to Transfer Hydrogenation to Hydrogen Auto-Transfer in Enantioselective Metal-Catalyzed Carbonyl Reductive Coupling: Past, Present, and Future.

Atom-efficient processes that occur via addition, redistribution or removal of hydrogen underlie many large volume industrial processes and pervade all segments of chemical industry. Although carbonyl addition is one of the oldest and most broadly utilized methods for C-C bond formation, the delivery of non-stabilized carbanions to carbonyl compounds has relied on premetalated reagents or metallic/organometallic reductants, which pose issues of safety and challenges large volume implementation. Catalytic carbonyl reductive couplings promoted via hydrogenation, transfer hydrogenation and hydrogen auto-transfer allow abundant unsaturated hydrocarbons to serve as substitutes to organometallic reagents, enabling C-C bond formation in the absence of stoichiometric metals.