Ketene-S,S-acetals as 1,3-dipolarophiles towards azides. A new synthetic entry into cyclic amino acids
摘要:
Intramolecular azide cycloaddition reactions of ketene-S,S-acetals proceed to give a reactive imine as the initially-formed intermediate and this mechanism is supported by thermolysis of (18) which gave the stable imine (22). N-Acylation of this intermediate leads to cyclic variants of 2-amino ketene-S,S-acetals (20, 24, 27), which can be viewed as masked alpha-amino acids, and reduction leads to the corresponding dithiane (21, 25, 29a). Both systems have been converted to cyclic alpha-amino acids and the scope, in terms of the ring sizes available, and the limitations of this intramolecular cycloaddition process are discussed.
The ketene thioacetal group as a cationic cyclization terminator.
作者:A.Richard Chamberlin、John Y.L. Chung
DOI:10.1016/s0040-4039(00)87412-2
日期:1982.1
A cationic cyclization to the pyrrolizidine ring system is reported in which a ketenethioacetal group serves as an efficient terminator for 5-membered ring formation. (±)-Supinidine is prepared using this methodology.