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J Am Chem Soc. 2009 Jan 28;131(3):878-9. doi: 10.1021/ja809220j.

Catalytic homologation of cycloalkanones with substituted diazomethanes. Mild and efficient single-step access to alpha-tertiary and alpha-quaternary carbonyl compounds.

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  • 1Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, Massachusetts 02467, USA.


Though volatile, toxic, and unstable, diazomethane is an indispensable one-carbon reagent with manifold uses in chemical synthesis. In this work, known protocols for hydrazone oxidation were adapted to permit facile access to a range of mono- and disubstituted aryl- or alkyldiazomethanes in pure form in solution; such procedures proceed in 30-60% overall yield starting from inexpensive carbonyl compounds. More important is the discovery that commercial Sc(III) salts are efficient catalysts for net insertion of the diazoalkyl carbon in these nucleophiles into the carbonyl C-C bond of simple cycloalkanones. In a single step, these reactions (1) forge two new C-C bonds under mild conditions, (2) produce molecular nitrogen as the sole stoichiometric byproduct, and (3) afford high yields of complex alpha-tertiary and -quaternary cyclic ketones that are typically accessible only through multistep procedures.

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