Hydride-Transfer Domino Rearrangement of Glycine-Containing Dioxa-azawurtzitane

Abstract

The novel synthetic method for dioxa-azawurtzitanes to selectively cap amino groups in amino acids or peptides is described. Mixing the CH(3)CN solution of cis,cis-1,3,5-triformyl-1,3,5-trimethylcyclohexane (2) with the aqueous solution of the equimolar amounts of glycine and NaHCO(3) yields glycine-containing dioxa-azawurtzitane 7-Na. Dioxa-azawurtzitane 7-Na almost quantitatively isomerizes to lactone-imine 9-Na through the hydride-transfer rearrangement in CH(3)CN/H(2)O. Lactone-imine 9-Na also isomerizes to lactam-aldehyde 12-Na in DMSO.

Determination of Molecular Stereochemistry Using Vibrational Circular Dichroism Spectroscopy: Absolute Configuration and Solution Conformation of 5‐Formyl‐cis, cis‐1,3,5‐trimethyl‐3‐hydroxymethylcyclohexane‐1‐carboxylic Acid Lactone

“…Derivatives of cis,cis ‐1,3,5‐trimethylcyclohexane‐1,3,5‐tricarboxylic acid (Kemp's triacid)30 have been used as a versatile molecule for molecular recognition studies 31–36. We have synthesized unique scaffolds from Kemp's triacid to utilize the synergistic effects of numerous functional groups upon the reactions of other neighboring groups 37–40. Recently, we reported the interaction of adjacent hydroxymethyl, formyl, and carboxyl groups 41.…”