I. The Stereochemistry of the Opening of the Imine Ring with Various Reagents. II. The Attempted Reduction of Naturally Occurring Threonine to 3-Amino-2-Butanol

Citation

Ghirardelli, Robert George (1956) I. The Stereochemistry of the Opening of the Imine Ring with Various Reagents. II. The Attempted Reduction of Naturally Occurring Threonine to 3-Amino-2-Butanol. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/AF4V-BN43. https://resolver.caltech.edu/CaltechETD:etd-03232004-104542

Abstract

The 2,3-iminobutanes react with acetic acid to give products that are easily converted without isolation into 3-acetamido-2-acetoxybutanes. Comparisons of the latter with samples of known configuration demonstrate that ring opening occurs in a trans manner. Attempts to prepare 3-p-toluenesulfonamido-2-p-toluenesulfonoxybutane by reaction of 2,3-iminobutane with p-toluenesulfonic acid, followed by treatment with p-toluenesulfonyl chloride, have failed. Under mild conditions the ring is not attacked, and under strenuous conditions elimination of ammonia occurs. The ring of the N-ethyl-2,3-iminobutanes, as well as that of the simple 2,3-iminobutanes, is opened by aqueous ammonia and ethylamine at elevated temperatures to give products which demonstrate that an inversion occurs. Many new imines, amino alcohols, and diamines have been synthesized. They are described, along with some of their derivatives. Both DL- and naturally occurring threonine have been reduced to derivatives of the corresponding 2-amino-1,3-butanediols. Attempts to reduce the latter to derivatives of the 3-amino-2-butanols have not yet succeeded.

Thesis Files