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Concept
Persistent carbene
Summary
A persistent carbene (also known as stable carbene) is a type of carbene demonstrating particular stability. The best-known examples and by far largest subgroup are the N-heterocyclic carbenes (NHC) (sometimes called Arduengo carbenes), for example diaminocarbenes with the general formula (R2N)2C:, where the four R moieties are typically alkyl and aryl groups. The groups can be linked to give heterocyclic carbenes, such as those derived from imidazole, imidazoline, thiazole or triazole.
Traditionally carbenes are viewed as so reactive that were only studied indirectly, such as by trapping reactions. This situation has changed dramatically with the emergence of persistent carbenes. Although they are fairly reactive substances, undergoing dimerization, many can be isolated as pure substances.
Persistent carbenes tend to exist in the singlet. Their stability is only partly due to steric hindrance by bulky groups. Some singlet carbenes are thermodynamically stable and can be isolated and indefinitely stored. Others dimerise slowly over days. Triplet state carbenes have half-lives measured in seconds, and therefore can be observed but not stored.
In 1957, Ronald Breslow proposed that a relatively stable nucleophilic carbene, a thiazol-2-ylidene derivative of vitamin B1 (thiamine), was the catalyst involved in the benzoin condensation that yields furoin from furfural.
In this cycle, the vitamin's thiazolium ring exchanges a hydrogen atom (attached to carbon 2 of the ring) for a furfural residue. In deuterated water, the C2-proton was found to rapidly exchange for a deuteron in a statistical equilibrium.
This exchange was proposed to proceed via intermediacy of a thiazol-2-ylidene. In 2012 the isolation of the so-called Breslow intermediate was reported.
In 1960, Hans-Werner Wanzlick and coworkers conjectured that carbenes derived from dihydroimidazol-2-ylidene were produced by vacuum pyrolysis of the corresponding 2-trichloromethyl dihydroimidazole compounds with the loss of chloroform.
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