| In this thesis, a review regarding the syntheses of six and seven-membered carbocycles from sugars via the intramolecular nitrone-alkene cycloaddition (INAC) pathway from 1976 to 2006 is presented.;To investigate the effect of blocking groups and stereochemistry of the substituents on the regio- and stereo selectivity in INAC reaction, eighteen hept-6-enoses were prepared from mono saccharides. The regio- and stereochemical outcome of the INAC reactions of hep-6-enoses were found to be significantly affected by the blocking group and the stereochemistry of the substituents. Hept-6-enose nitrone containing a 2,3-cis-isopropylidene ring (nitrones 93 and 96) afforded exo-cycloadducts (cyclohexanes) exclusively. On the other hand, full attainment of endo-cycloadducts (cycloheptanes) was realized with a 3,4-trans-isopropylidene ring (nitrones 175, 181, 190, 195, 200, 213, and 222). The bridged bicyclo[4.2.1] isoxazolidines, via the endo mode of INAC reaction, were synthesized for the first time from unbranched sugar derivatives. The regio- and stereo-chemical outcomes of these reactions were rationalized on the basis of transition state energies obtained by computation.;The polyhydroxylated cyclohexanes and cycloheptanes constructed from sugars via the INAC approach were successfully transformed into a variety of target molecules including pseudoaminosugars, calystegine and tropane analogues. Three pseudo-4-aminopyranoses 242, 260 and 265 were synthesized from bicyclo[4.3.0] systems. With bicyclo[4.2.1] systems, ( S)-3-hydroxy-calystegine B5 280, 1-deoxy-calystegine C1 296 (a tropane skeleton) and three B-type calystegine analogues 274, 282, and 289 were harvested. Conversions of three aminocycloheptanols 299, 300, and 301 from the bridged bicyclo[4.2.1] systems were also successful.;Another type of the 1,3-dipolar cycloaddition, the intramolecular nitrile oxidealkene cycloaddition (INOC) was studied with hept-6-enoses having a free hydroxyl group. The INOC reaction, by incorporating chloramine-T and silica gel for the formation of nitrile oxide from hept-6-enose oxime, proceeded smoothly with an unmasked hydroxyl group to give cyclohexanes. |
