Inositols belong to an important class of biologically active compounds, named as cyclitols (cyclic polyols), which have attributed high interest in the past decade due to the glycosidase inhbition property that affects many biological processes. Initially, 1,3,3a,7a-tetrahydro-2-benzofuran (69) was synthesized as a key compound to synthesize bishomo-inositol derivatives. Then photooxygenation and manganese(III) acetate oxidation reactions of this key compound were studied in order to obtain isomeric inositol derivatives. Moreover, dihydroxylation and acid catalyzed ring opening reactions were investigated. Finally, new synthetic approaches for the synthesis of bishomo-inositol derivatives have been developed. In addition to that whole products were conscientiously purified and characterized and mechanism for the formation of the products has been discussed.