The chromous chloride promoted addition of N-haloamides to olefins. V. The addition of N-chloroamides to enol ethers: synthesis of acyloxy and acyl derivatives of α-amino acetals and ketals (aldehydes and ketones) and of 2-amino sugars

Abstract

The chromous chloride promoted addition of N-chlorocarbamates and N-chlorocarboxamides to 1-methoxycyclohexene, ethoxyethylene, dihydropyran, and (1-methoxyethylidene)-cyclohexane gave, in 60 to 85% yields, either α-acyloxy- or α-acylamino ketals and acetals, or the corresponding ketones and aldehydes depending on the work-up conditions. The regio-specificity of the addition was higher with the first two enol ethers (≥97%) than with the latter two (≥85%). N-Chlorourethane was added to 17-methoxymethylenandrost-4-en-3-one (19) and the sole addition product isolated was the 17α-chloro-20-ethoxycarbonylamino derivative 20 in 75% yield. Additions to triacetyl-D-glucal and 3-O-acetyl-4,6-O-benzylidene-D-glucal followed by solvolysis under Koenigs–Knorr conditions led predominantly to 2-amino-gluco-pyranosides in 30 to 65% yields, whereas additions to 3-O-acetyl-4,6-O-benzylidene-D-allal gave 2-amino altropyranosides in 40 to 56% yields.