A dinickel-catalyzed three-component cycloaddition of vinylidenes.

A dinickel catalyst promotes the [2 + 2 + 1]-cycloaddition of two aldehyde equivalents and a vinylidene. The resulting methylenedioxolane products can be deprotected in one pot under acidic conditions to reveal α-hydroxy ketones. This method provides convenient access to unsymmetrical alkyl-substituted α-hydroxy ketones, which are challenging to synthesize selectively using cross-benzoin reactions. Mechanistic studies are consistent with an initial migratory insertion of the aldehyde into a dinickel bridging vinylidene. Insertion of the second aldehyde followed by C-O reductive elimination furnishes the cycloadduct. Under dilute conditions, an enone side product is generated due to a competing ß-hydride elimination from the proposed metallacyclic intermediate. A DFT model consistent with the concentration-dependent formation of the methylenedioxolane and enone is presented.

Catalytic Reductive Carbene Transfer Reactions.

Efforts to develop catalytic carbene transfer reactions have largely relied on the use of diazo precursors. However, diazoalkanes are susceptible to undergoing violent exothermic decomposition unless they contain stabilizing substituents. Consequently, most synthetic methods are restricted to diazoacetates or related derivatives. In this Perspective, we describe an alternative approach to carbene transfer catalysis based on the generation of metal carbenoids from gem-dihaloalkanes and gem-dihaloalkenes. These precursors are readily available and stable in unsubstituted form or with a variety of donor and acceptor substituents. Using this approach, it is possible to design cyclopropanation reactions with non-stabilized carbenes, such as methylene, isopropylidene, and vinylidene. Furthermore, due to the distinct mechanistic pathways of these reactions, novel modes of cycloaddition can be carried out, including [4 + 1]-cycloadditions.

Dinickel Catalyzed Vinylidene-Alkene Cyclization Reactions.

A dinickel catalyst promotes reductive cyclization reactions of 1,1-dichloroalkenes containing pendant olefins. The reactions can be conducted with a Zn reductant or electrocatalytically using a carbon working electrode. Mechanistic studies are consistent with the intermediacy of a Ni2(vinylidene) species, which adds to the alkene and generates a metallacyclic intermediate. ß-Hydride elimination followed by C-H reductive elimination forms the cyclization product. The proposed dinickel metallacycle is structurally characterized and its stoichiometric conversion to product is demonstrated. Spin polarized, unrestricted DFT calculations are used to further examine the cyclization mechanism. These computational models reveal that both nickel centers function cooperatively to mediate the key oxidative addition, migratory insertion, ß-hydride elimination, and reductive elimination steps.

A Dinickel Catalyzed Cyclopropanation without the Formation of a Metal Carbene Intermediate.

(NDI)Ni2 catalysts (NDI=naphthyridine-diimine) promote cyclopropanation reactions of 1,3-dienes using (Me3 Si)CHN2 . Mechanistic studies reveal that a metal carbene intermediate is not part of the catalytic cycle. The (NDI)Ni2 (CHSiMe3 ) complex was independently synthesized and found to be unreactive toward dienes. Based on DFT models, we propose an alternative mechanism that begins with a Ni2 -mediated coupling of (Me3 Si)CHN2 and the diene. N2 extrusion followed by radical C-C bond formation generates the cyclopropane product. This model reproduces the experimentally observed regioselectivity and diastereoselectivity of the reaction.