Electrophilic reactivity, lithium carbenoids

The particular substitution pattern of lithium carbenoids, the fact that both an electropositive metal and an electronegative substituent X are bound to the same carbon atom, causes the ambiphilic character of this species. The chameleon-like reactivity becomes evident from the resonance formulas of the carbenoid lb (equation 1) Whereas the carbanionic character is expressed by the resonance formula la, the electrophilic character is represented by Ic. In an analogous way, the reactivity of vinylidene carbenoids 2b is expressed by the mesomeric structures 2a and 2c. 

The electrophilic reactivity of lithium carbenoids (reaction b) becomes evident from their reaction with alkyl lithium compounds. A, probably metal-supported, nucleophilic substitution occurs, and the leaving group X is replaced by the alkyl group R with inversion of the configuration . This reaction, typical of metal carbenoids, is not restricted to the vinylidene substitution pattern, but occurs in alkyl and cycloalkyl lithium carbenoids as well ". With respect to the a-heteroatom X, the carbenoid character is... 

Organolithium compounds which bear a lithium atom as well as a leaving group such as a halogen atom or an alkoxy group on the same carbon atom — lithium carbenoids — are a well-characterized class of compounds [1-5]. They react as nucleophiles or electrophiles depending on the chosen conditions the electrophilic reactivity is typical of carbenoids. 

Mixed bimetallic reagents possess two carbon-metal bonds of different reactivity, and a selective and sequential reaction with two different electrophiles should be possible. Thus, the treatment of the l,l-bimetailic compound 15 with iodine, at — 78"C, affords an intermediate zinc carbenoid 16 that, after hydrolysis, furnishes an unsaturated alkyl iodide in 61% yield [Eq. (15) 8]. The reverse addition sequence [AcOH (1 equiv), —80 to — 40 C iodine (1 equiv)] leads to the desired product, with equally high yield [8]. A range of electrophile couples can be added, and the stannylation of 15 is an especially efficient process [Eq. (16) 8]. A smooth oxidation of the bimetallic functionality by using methyl disulfide, followed by an acidic hydrolysis, produces the aldehyde 17 (53%), whereas the treatment with methyl disulfide, followed by the addition of allyl bromide, furnishes a dienic thioether in 76% yield [Eq. (17) 8]. The addition of allylzinc bromide to 1-octenyllithium produces the lithium-zinc bimetallic reagent 18, which can be treated with an excess of methyl iodide, leading to only the monomethylated product 19. The carbon zinc bond is unreactive toward methyl iodide and, after hydrolysis, the alkene 19... 

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