The mechanism of cobalt(II)-porphyrin-mediated cyclopropanation of olefins with diazoesters was studied. The first step--reaction of cobalt(II)-porphyrin with ethyl diazoacetate (EDA)--was examined using EPR and ESI-MS techniques. EDA reacts with cobalt(II)-porphyrin to form a 1:1 Co(por)(CHCOOEt) adduct that exists as two isomers: the 'bridging carbene' C' in which the 'carbene' is bound to the metal and the pyrrolic nitrogen of the porphyrin that has a d(7) configuration on the metal, and the 'terminal carbene' C in which the 'carbene' behaves as a redox noninnocent ligand having a d(6) cobalt center and the unpaired electron residing on the 'carbene' carbon atom. The subsequent reactivities of the thus formed 'cobalt carbene radical' with propene, styrene, and methyl acrylate were studied using DFT calculations. The calculations suggest that the formation of the carbene is the rate-limiting step for the unfunctionalized Co(II)(por) and that the cyclopropane ring formation proceeds via a stepwise radical process: Radical addition of the 'carbene radical' C to the C=C double bonds of the olefins results in formation of the gamma-alkyl radical intermediates D. Species D then easily collapse in almost barrierless ring-closure reactions (TS3) to form the cyclopropanes. This radical mechanism readily explains the high activity of Co(II)(por) species in the cyclopropanation of electron-deficient olefins such as methyl acrylate.
Unprecedented rhodium-catalyzed stereoselective polymerization of "carbenes" from ethyl diazoacetate (EDA) to give high molecular mass poly(ethyl 2-ylidene-acetate) is described. The mononuclear, neutral [(N,O-ligand)M(I)(cod)] (M = Rh, Ir) catalytic precursors for this reaction are characterized by (among others) single-crystal X-ray diffraction. These species mediate formation of a new type of polymers from EDA: carbon-chain polymers functionalized with a polar substituent at each carbon of the polymer backbone. The polymers are obtained as white powders with surprisingly sharp NMR resonances. Solution and solid state NMR data for these new polymers reveal a highly stereoregular polymer, with a high degree of crystallinity. The polymer is likely syndiotactic. Material properties are very different from those of atactic poly(diethyl fumarate) polymer obtained by radical polymerization of diethyl fumarate. Other diazoacetates are also polymerized. Further studies are underway to reveal possible applications of these new materials.
In this Forum contribution, we highlight the radical-type reactivities of one-electron-reduced Fischer-type carbenes. Carbene complexes of group 6 transition metals (Cr, Mo, and W) can be relatively easily reduced by an external reducing agent, leading to one-electron reduction of the carbene ligand moiety. This leads to the formation of "carbene-radical" ligands, showing typical radical-type reactivities. Fischer-type carbene ligands are thus clearly redox-active and can behave as so-called "redox noninnocent ligands". The "redox noninnocence" of Fischer-type carbene ligands is most clearly illustrated at group 9 transition metals in the oxidation state II+ (Co(II), Rh(II), and Ir(II)). In such carbene complexes, the metal effectively reduces the carbene ligand by one electron in an intramolecular redox process. As a result, the thus formed "carbene radicals" undergo a variety of radical-type C-C and C-H bond formations. The redox noninnocence of Fischer-type carbene ligands is not just a chemical curiosity but, in fact, plays an essential role in catalytic cyclopropanation reactions by cobalt(II) porphyrins. This has led to the successful development of new chiral cobalt(II) porphyrins as highly effective catalysts for asymmetric cyclopropanation with unprecedented reactivity and stereocontrol. The redox noninnocence of the carbene intermediates results in the formation of carbene-radical ligands with nucleophilic character, which explains their effectiveness in the cyclopropanation of electron-deficient olefins and their reduced tendency to mediate carbene dimerization. To the best of our knowledge, this represents the first example in which the redox noninnocence of a reacting ligand plays a key role in a catalytic organometallic reaction. This Forum contribution ends with an outlook on further potential applications of one-electron-activated Fischer-type carbenes in new catalytic reactions.
This tutorial review provides a comparison between the concepts of catalytic decarboxylative and decarbonylative couplings for the ipso-substitution of carboxylate groups, and illustrates their potential benefits over alternative C-C bond-forming reactions. Redox-neutral decarboxylative reactions allow generating organometallic species with nucleophilic reactivity via the extrusion of carbon dioxide from metal carboxylates. Such C-C bond activating processes provide a way of employing carboxylate salts as substitutes for the traditional sources of carbon nucleophiles, i.e. stoichiometric organometallic reagents. If the decarboxylation of carboxylic acids is performed under oxidative conditions, organometallic species with electrophilic reactivity are obtained instead. These can alternatively be accessed via the extrusion of carbon monoxide from acyl-metal species generated via the oxidative addition of activated carboxylic acid derivatives (e.g. acid chlorides, anhydrides or esters) to metal complexes. In the latter two reaction types, carboxylic acids thus become substitutes for organohalides. The complementary redox-neutral and oxidative decarboxylative and decarbonylative reaction modes allow the broad use of carboxylic acids as substrates in C-C bond-forming reactions. Their applicability, scope and limitations are discussed using the examples of Heck reactions, cross-couplings and direct arylations.
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