Transformations of some nickel tetrahydrocorrin tertiary esters

Abstract

LiAlH4 reduction of tertiary ester groups at C–1, C–2, or C–3 in a nickel tetradehydrocorrin results in rapid elimination of the substituent; methylation of the 1-monoester occurs at C–19 and subsequent removal of the ester gives the nickel 1-methyltetradehydrocorrin; rearrangement of the ester group at C–1 to C–2 in neutral nickel tetrahydrocorrins is rapid even at room temperature, and when the product is heated a further rearrangement of the ester to C–3 takes place.