Synthesis of 2-(5',5'-Ethylenedioxy-1'-methylcyclopent-2'-en-1'-yl)ethanol, and Some 2H-Cyclopenta[b]furan Derivatives Formed by Intramolecular Displacement Reactions

Abstract

Exchange dioxolanation of 2-methyl-2-(prop-2′-enyl)cyclopentane-1,3-done (1b) gave 3,3- ethylenedioxy-2-methyl-2-(prop-2′-enyl) cyclopentan-1-one (2) which, upon reduction and esterification , afforded the epimeric 3,3-ethylenedioxy-2-methyl-2-(prop-2′-enyl) cyclopent-1-yl benzoates (6d). Oxidative cleavage of the terminal double bond in (6d),followed by sodium borohydride reduction yielded 3,3-ethylenedioxy-2-(2'-hydroxyethyl)-2-methylcyclopent-1-yl benzoate (4b) which underwent acid- catalysed rearrangement to 6a-(2′-hydroxyethoxy)-3a- methylhexahydrocyclopenta [b]furan-4-yl benzoate (8b). Flash vacuum pyrolysis of the t- butyldimethylsilyl ether (12), derived from the hydroxy acetal (4b), afforded 3-[2′- (t- butyldimethylsilyloxy )ethyl]-4,4-ethy1enedioxy-3-methylcyclopent-1-ene (14) which upon selective cleavage of the silyl ether group gave 2-(5′,5′-ethylenedioxy-1′-methylcyclopent- 2'′en-1′-y1)ethanol (7). Reaction of the mesylate (16) of (7) with lithium bromide or iodide in tetrahydrofuran at 50-55º for several hours yielded some of the corresponding 3-(2′-haloethyl) compounds (17), but gave mainly the rearranged 6a-(2′-haloethoxy)-3a-methyl-3,3a,6,6a-tetrahydro-2H-cyclopenta[b]furans (19a) and (19b). Some related chemistry is described.