Newly designed and prepared vanadium complexes bearing anionic pyrrole-based PNP-type pincer and aryloxy ligands were found to work as effective catalysts for the direct conversion of molecular dinitrogen into ammonia and hydrazine under mild reaction conditions. This is the first successful example of vanadium-catalyzed dinitrogen reduction under mild reaction conditions.

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Iron-dinitrogen complexes bearing methyl- and phenyl-substituted pyrrole-based anionic PNP-type pincer ligands are prepared and characterized by X-ray analysis. The former complex is found to work as a more effective catalyst than that bearing a non-substituted PNP-type pincer ligand toward the transformation of nitrogen gas into ammonia and hydrazine under mild reaction conditions.

Dinitrogen-bridged dititanium and dizirconium complexes bearing anionic pyrrole-based PNP-type pincer ligands are prepared and characterized by X-ray analysis. Their catalytic activity is investigated toward reduction of nitrogen gas into ammonia and hydrazine under mild reaction conditions.

We report herein cobalt-catalyzed enantioselective and chemodivergent reactions between a cyclopropanol and an oxabicyclic alkene via a cobalt homoenolate, which afford either an alkylative ring-opening product or a hydroalkylation product, with the counterion of the cobalt catalyst being a major chemoselectivity-controlling factor. A catalyst generated from cobalt­(II) chloride and a chiral diphosphine promotes alkylative ring opening to afford 1,2-dihydronaphthalen-1-ol derivatives in good yields with high enantioselectivity. By contrast, a catalyst generated from cobalt­(II) acetate and the same diphosphine ligand, with the assistance of methanol, selectively affords hydroalkylation products with retention of the bicyclic structure at a comparable level of enantioselectivity.

We report herein an enantioselective conjugate addition reaction of a zinc homoenolate, catalytically generated via ring opening of a cyclopropanol, to an α,β-unsaturated ketone. The reaction is promoted by a zinc aminoalkoxide catalyst generated from Et2Zn and a chiral β-amino alcohol to afford 1,6-diketones, which undergo, upon heating, intramolecular aldol condensation to furnish highly substituted cyclopentene derivatives with good to high enantioselectivities. The reaction has proved applicable to various 1-substituted cyclopropanols as well as chalcones and related enones. The chiral amino alcohol has proved to enable ligand-accelerated catalysis of the homoenolate generation and its conjugate addition. Positive nonlinear effects and lower reactivity of a racemic catalyst have been observed, which can be attributed to a stable and inactive heterochiral zinc aminoalkoxide dimer. File list (2) download file view on ChemRxiv SI_ZnHomoenolate_YS.pdf (16.62 MiB) download file view on ChemRxiv ZnHomoenolate_YS.pdf (1.01 MiB)

We report herein a nickel-catalyzed ring-opening allylation of cyclopropanols with allylic carbonates that occurs under mild and neutral conditions. The reaction displays linear selectivity for both linear and branched acyclic allylic carbonates and is also applicable to cyclic allylic carbonates, affording a variety of δ,ε-unsaturated ketones in moderate to good yields. Mechanistic experiments are in accord with a catalytic cycle involving decarboxylative oxidative addition of allylic carbonate to Ni(0), alkoxide exchange with cyclopropanol, cyclopropoxide-to-homoenolate conversion on Ni­(II), and C–C reductive elimination.

Direct and diastereoselective synthesis of vicinal anti-sec,tert-diols has been achieved by zinc-mediated α-hydroxyallylation of aldehydes with cyclopropanols. The reaction features the action of the zinc-enolized homoenolate as a γ-oxyallyl nucleophile toward the carbonyl electrophile. The diastereoselectivity of the present reaction is ascribed to the strong preference for a chelated (Z)-configuration of the enolized homoenolate as well as the bicyclic chairlike transition state it forms with the aldehyde, where the aldehyde substituent prefers to occupy the pseudoaxial position.