Thiazole constrained analogues of the thevinones: synthesis and structure.

ABSTRACT

A simple synthesis of ring-constrained endoethenomorphinans possessing 2'-substituted thiazole ring 4-6 has been achieved by regio- and stereoselective Diels-Alder reaction of thiazolomorphinandienes 1-3 and methyl vinyl ketone in high yield (72, 64 and 87%, respectively). The structure of cycloaddition products was determined by high resolution mass spectrometry (HRMS), IR, 1D and 2D NMR techniques. Double-pulsed field gradient spin-echo-nOe and HMBC were found to be particularly powerful and indispensable tools in the exact structural elucidation of the presented new class of spatially constrained thevinones.