Russell C. Klix

On the geometric requirements for concerted 1,2-carbonyl migration in α,β-epoxy ketones

Abstract The stabilizing influence of neighboring group participation by the carbonyl group in concerted 1,2-acyl migration is related to the ability of the molecule to assume a transition stage geometry resembling a cyclopropyloxenium ion.

Model studies aimed at the synthesis of Fredericamycin A. A simple o-quinodimethane route to the spiro naphthalene portion

Abstract The three contiguous rings in the naphthalene portion of a model compound related to Fredericamycin A have been prepared by the Diels-Alder cycloaddition reaction of an α-bromo-o-quinodimethane intermediate to the carbon—carbon double bond of the spiro dienophile, spiro[4.4]non-2, 3-ene-1, 4-dione.

Lewis acid catalyzed rearrangements of structurally related α,β-unsaturated epoxy ketones and oximes. A complementary approach to the synthesis of isomeric 1,4-diketospiro[n,m] alkanes.

Abstract Lewis acid catalyzed rearrangement of α,β-epoxy oximes proceeds by oxirane cleavage α to the oxime moiety with an attendant pinacol type alkyl migration to the resonance stabilized carbenium ion at C α , affording a 1,3-diketo-monoxime.

A practical, large-scale procedure for the preparation of N-protected α-amino ketones from α-amino acids

Abstract A convenient multigram-scale method has been developed for the preparation of chiral N-protected α-amino ketones from chiral N-protected amino acids. Several examples using this procedure are reported, including a large scale application.

SYNTHESIS OF 5,6-METHYLENEDIOXY-1-TETRALONE. AN ARYL GRIGNARD APPROACH FROM GUAIACOL

A convenient synthesis of 5,6-methylenedioxy-1-tetralone (1) is described. The main features of this synthesis are the formation of 6 via a Grignard reaction using succinic anhydride followed by selective reduction and Friedel-Crafts cyclization to generate the desired tetralone 1.