From Sugars to Carbocycles. 2. Three- to Seven-Membered Rings from Mannose by Addition of 1,3-Dithiane Followed by Intramolecular Displacement Reaction

Article abstract of DOI:10.1021/jo00099a043

A new methodology for the conversion of sugars to three-, four-, six-, and seven-membered rings is presented.The sequence of transformations is demonstrated with mannose (1) and involves addition of 2-lithio-1,3-dithiane to the acetonide 2 followed by elimination and reduction to the 2-deoxydithiane 6.Starting from this intermediate, appropriate activation (tosylate, epoxide) and protection (acetonide, methyl ether) yields 8, 18, and 23, the starting materials for carbocyclization, which are converted by nucleophile displacement to the optically active cyclopropane 9, cyclobutane 19, cyclohexane 24, and cycloheptane 25, respectively.The cyclopropyl-1,3-dithiane 9 can be desulfurized to the cyclopropane 10.