Synthesis and rearrangement reactions of 1,4-dihydrospiro[1,4-methanonaphthalene-9,1′-cyclopropane] derivatives

Abstract Reactions of benzyne with ester derivatives of spiro[2.4]hepta-4,6-dien-1-ylmethanol were performed. By rearrangement reaction of cyclopropyl methanol units of ((1s*,1′R*,2R*,4′S*)-1′,4′-dihydrospiro[cyclopropane-1,9'-[1,4]methanonaphthalen]-2-yl) methyl 3,5- dinitrobenzoate ( 13 ) and its isomer ( 14 ), corresponding allyl chlorides were obtained. Two rearrangement products were obtained from bromination of compound 13 with an equivalent amount of Br 2 . A naphthalene derivative including allyl and CHO moiety was formed for reactions from compounds with epoxide of 13 and 14 with NaN 3 by sequential rearrangements. Formations of products are discussed.