Cyclic carbenes mechanism

The kinetics and mechanism of pyrrole pyrolysis were investigated by ab initio quantum-chemical calculations. It was revealed that pyrrole undergoes tautomerization to form 2H- and 37/-pyrroles prior to any thermal decomposition. It has been shown that the major product, HCN, arises from a hydrogen migration in pyrrole to form a cyclic carbene with the NH bond intact. Ring scission of the carbene leads to an allenic imine of HCN and propyne which is the lowest energy pathway. The 277-pyrrole... 

A detailed quantum mechanical study of the mechanism of thermal decomposition of isoxazole has been conducted since previous theoretical predictions appeared to be inconsistent with the experimental results.33 It has been concluded that the mam unimolecular decomposition is through the sequence isoxazole —> NCCH2CHO —> CH3CN + CO and that the minor products, HCN and H2CCO, probably arise via a cyclic carbene as proposed in the experimental study. 

The suggestion that a metal carbene was the active metal-containing species involved in the reaction inspired an impressive number of elegant experiments, designed to test the vahdity of this mechanism. The results of double crossover experiments as well as isotopic labeling experiments showed conclusively that a pairwise mechanism could not account for the observed data. The reaction shown in equation (5) shows the possible products of the metathesis of two isotopically labeled dienes, and these products include a cyclic alkene derived from the closing of the diene as well as a series of deuterated ethylenes. At very low conversions, the observed ratio of ethylenes was 1 2 1 dQ d.2.d ). A detailed analysis of these results demonstrated that the pairwise mechanism could not possibly account for this result, while the carbene mechanism could. 

The operative mechanism is a matter of debate and would seem to be substrate dependant. For instance, it is believed that THF coordinates to the metal prior to successive jS-, then a-hydride eliminations, a notion that is also invoked for the activation of MeOPh, EtOPh and Me2NPh by 238. It is argued for these cases that carbene formation precedes the cyclometallation step, which is less strained for the carbene-bound ring than for the Tp phenyl group hence the preferential formation of cyclic carbenes 489, 490 and 498 over K -N,N, N",C-Tip analogues of 488, 491 and 497. However, the activation of Me2NPh by 211 was independently... 

In the case of cycloocta-1,5-diene the series of cyclic oligomers have the formula (C4Hg) (n = 4-13) with no tendency for the even-numbered members of the series to predominate, one of the observations that led Herisson and Chauvin to the proposal of the metal carbene mechanism. 

The two-step process, depicted by path b, involves initial addition of the carbene carbon to an adjacent it bond to form bicyclo[4.1,0]hepta-2,4,6-triene (2a). This process has precedent in the analogous rearrangement of vinylcar-bene to cyclopropene (Scheme 6),lc18 and is supported by Gaspar s work on 1-cyclohexenylcarbene.17 In the second step of the mechanism in Scheme 5, subsequent six-electron electrocyclic ring opening of 2a yields the cyclic allene 3a. 

The product is exclusively carbon monoxide, and good turnover numbers are found in preparative-scale electrolysis. Analysis of the reaction orders in CO2 and AH suggests the mechanism depicted in Scheme 4.6. After generation of the iron(O) complex, the first step in the catalytic reaction is the formation of an adduct with one molecule of CO2. Only one form of the resulting complex is shown in the scheme. Other forms may result from the attack of CO2 on the porphyrin, since all the electronic density is not necessarily concentrated on the iron atom [an iron(I) anion radical and an iron(II) di-anion mesomeric forms may mix to some extent with the form shown in the scheme, in which all the electronic density is located on iron]. Addition of a weak Bronsted acid stabilizes the iron(II) carbene-like structure of the adduct, which then produces the carbon monoxide complex after elimination of a water molecule. The formation of carbon monoxide, which is the only electrolysis product, also appears in the cyclic voltammogram. The anodic peak 2a, corresponding to the reoxidation of iron(II) into iron(III) is indeed shifted toward a more negative value, 2a, as it is when CO is added to the solution. 

Reactions of alkynyliodonium salts 119 with nucleophiles proceed via an addition-elimination mechanism involving alkylidenecarbenes 120 as key intermediates. Depending on the structure of the alkynyliodonium salt, specific reaction conditions, and the nucleophile employed, this process can lead to a substituted alkyne 121 due to the carbene rearrangement, or to a cyclic product 122 via intramolecular 1,5-carbene insertion (Scheme 50). Both of these reaction pathways have been widely utilized as a synthetic tool for the formation of new C-C bonds. In addition, the transition metal mediated cross-coupling reactions of alkynyliodonium salts are increasingly used in organic synthesis. 

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