Carbenes are unique reactive intermediates that are useful in organic synthesis. With only two bonding partners and two free electrons, these low-valent carbon species are often highly reactive, and can be ambiphilic in the singlet state, possessing the ability to behave as both nucleophiles and electrophiles. β-Heteroatom-stabilized carbenes are a class of carbene that has gone largely unutilized. Their reactivity is defined by an anionic β-heteroatom that interacts with the carbene center, and influences the carbene reactivity. Only carboxylate carbenes have been previously studied, but their use in synthesis has not yet been realized. Predicted to exist in the singlet state, β-heteroatom-stabilized carbenes are unique among other carbonyl carbenes for their nucleophilicity. We envision that this unique reactivity can be used for synthetic gain and are exploring several strategies to both α-diazoamides and α-diazoacids, the precursor to amidate and carboxylate carbenes. We will discuss these strategies and report on obstacles we have encountered. We will also detail a hydrazone oxidation study we have undertaken in an effort to obtain α-diazoacids.

Making the precursors to β-heteroatom-stabilized carbenes

2019 Spring National Meeting

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