Stereoselective Synthesis of Alcohols, L. Synthesis and Conformational Studies of 1,5‐Dioxa‐cis‐decalin

Abstract cis ‐2‐Vinyltetrahydropyran‐3‐ol ( 6 ) is accessible by a selective intramolecular allylboration reaction. Compound 6 was converted into 1,4‐dioxa‐ cis ‐decaline ( 4 ) and cis‐syn‐cis ‐perhydrotrioxaanthracene 32 ; heterocycles with fused tetrahydropyran rings. These ring systems populate predominantly the conformation in which the oxygen atoms are in a gauche arrangement. The tricycle 31 is a rigid derivative of 14‐crown‐3 and, as in the case of 12‐crown‐3, it forms complexes with lithium ions in acetonitrile.