Synthesis of anellated pyranose derivatives on the basis of levoglucosenone

1,6-Anhydro-2-(dicyanomethylene)-2,3-dideoxy-4-S-ethyl-4-thio-beta-D-erythro-hex opyranose (1) reacted with tosyl azide or sulfur and triethylamine to furnish the 5-aza-10,11-dioxatricyclo[6.2.1.0(2,6)]undeca-2(6),3-diene-3-carbonitrile 2 and the 10,11-dioxa-5-thiatricyclo[6.2.1.0(2,6)]undeca-2(6),3-diene-3-carbonitrile 3, respectively. The reactions of 1 with arylisothiocyanates furnished the 11,12-dioxa-5-thiatricyclo[7.2.1.0(2,7)]dodeca-2(7),3-diene-3-carbonitriles 4 an d 5. 3 underwent cyclization with triethyl orthoformate and ammonia or hydrazine hydrate to afford the 5,7-diaza-14,15-dioxa-9-thiatetracyclo[10.2.1.0(2,10).0(3.8)]pentadecatetra(tri) enes 7 and 8, respectively.