Abstract
1.4 E x p e rim e n ta l S ection ................................................................................. 19 1.4.1 Synthesis of Diethyl 2,3-0-isopropylidene-L-tartrate (1 .1 ) ................ 19 1.4.2 Synthesis of 2,3-0-isopropylidene-L-threitol (1.2) ........................... 20 1.4.3 Synthesis of l,46]deca-3,8-dione ( 2 .8 ) ...................... 58 2.4.9 Attempted synthesis of 3,8-te-(2,4-cyclopentadiene-l-ylidene) tricy c lo [5 .3 .0 .0 2,6]decane (2.9) .............. 58 2.4.10 Synthesis of tricyclo[6.2.1.02*7]undeca-4,9-diene-3,6-dione (2 .1 0 ) ........................................................................................................ 59 2.4.11 Synthesis of pentacyclo[5.4.0.02,603’1005'9]undeca-8,ll-dione (2 .1 1 ) ........................................................................................................ 59 2.4.12 Attempted Synthesis of 3,8-Ms-(2,4-cyclopentadiene-lylidene)pentacyclo[5.4.0.02*^03,1°05,9]undecane (2 .1 2 ) ................... 60 2.4.13 Synthesis of 2-oxo-(l-carboethoxy-r-ethylbutyrate) cyclopentane (2 .1 4 ) ............................................................................. 61 2.4.14 Synthesis of 2-oxo-l-cyclopentanebutyric acid (2.15) ...................... 62 2.4.15 Synthesis of spiro[4.4]nona-l,6-dione (2.16) ...................................62 2.4.16 Attempted synthesis of l,6-Wa-(2,4-cyclopentadiene-lylidene)spiro[4.4]nonane (2 .17) ....................................................... 63 2.4.17 Synthesis of 4,5-Ws-methyl-2,2-dimethyl-1,3-dioxolane4,5-rra«5-/?J5-carboxylate (2.18) ...................................................... 64 2.4.18 Synthesis of 4,5-6«-pyrrolidyiamide-2,2-dimethyl-1,3dioxolane (2 .19 ) ................................................................................ 64 2.4.19 Synthesis of 4,5-trans-bis-acetyl-2,2-dimethyl1,3-dioxolane (2 .2 0 ) ....................................................................................................... 65 2.4.20 Attempted synthesis of 4,5-rra/«-6/,s-l-(2,4-cyclopentadien-lylidene)ethyl-2,2-dimethyl-1,3-dioxolane (2.21) .............................. 66 2.4.21 Synthesis of l,r-binaphthyl-2,2'-&/A-naphthaldehyde (2 .2 2 ).......... 66 2.4.22 Attempted synthesis of l,r-binaphthyl-2,2'-fefv-(2,4cyclopentadien-l-ylidene) (2.23) ..................................................... 67 CH A PTER TH R EE . Synthesis o f Tricyclo[9.3.0.04>«]tetradeca 4 ,7 ,1 1 ,1 4 te t r a e n e 69 3.1 In tro d u c tio n .................................................................................................... 69 3.1 .1 Retrosynthetic Analysis ......................................................................... 70 3.1.1.1 Analysis via Thermal Interconversion (A) ................................. 70 3.1.1.2 Analysis via Diels-Alder Cyclocondensation ( B ) ...................... 72 3.1.2 Diels-Alder Cyclocondensation Reaction. A Brief Introduction............ 72 3.1.2.1 Stereoelectronic Effects in the Diels-Alder Cyclocondensation Reaction ............................................................................................... 73 3.1.2.1.1 Through-Bond Orbital Interactions ........................................ 75 3.1.2.1.2 Through-Space Orbital Interactions ................................. 77 3.2 R esu lts an d D iscussion ............................................................................... 81 3.2.1 Synthesis via Thermal Rearrangement ................................................. 81 3.2.2 Synthesis via Diels-Alder Cyclocondensation ................................... 86 3.2.2.1 Detailed Study of the Diels-Alder Cyclocondensation Reaction .... 94 3.3 C o n c lu s io n s .................................................................................................... 144 3.4 E x p e rim en ta l Section ............................................................................ 145 3 .4 .1 Synthesis of 2,2'-(p-toluensulfonylimino)fr/A’-ethyl-di(ptoluensulfonate) (3 .2) ......................................................................... 145 3.4.2 Synthesis of N-(p-toluenesulfonyl)-8-azaspirol4.5]deca-l,3diene (3 .3 ) .............................................................................................. 146 3.4.3 Synthesis of 2,2'-6i\s-(/J-toluensulfonyl)-diethylene glycol (3 .4 ) .......................................................................................................... 147 3.4.4 Synthesis of 8-Oxaspiro[4.5]decane-l,3-diene (3.5) ....................... 147 3.4.5 Attempted Synthesis of l-(2-Hydroxyethyl)-l-(2-bromoethyl)2,4-cyclopentadiene (3.6) ............................................................... 148 3.4.6 Synthesis of l,l-dimethoxy-2,3,4,5-tetrachlorocyclopentadiene (3 .8 ) 149