The hetero-Diels-Alder addition of sulfur dioxide to 1-fluorobuta-1,3-dienes: the sofa conformations preferred by 6-fluorosultines (6-fluoro-3,6-dihydro-1,2-oxathiin-2-oxides) enjoy enthalpic and conformational Anomeric effects.
The reactivity of (E)- and (Z)-1-fluorobuta-1,3-diene ((E)- and (Z)-11), 2-fluorobutadiene (12), (E)- and (Z)-1-(fluoromethylidene)-2-methylidenecyclohexane ((E)- and (Z)-13) toward SO(2) has been explored and compared with that of (Z)- and (E)-1-(fluoromethylidene)-2-methylidene-3,4-dihydronaphthalene ((Z)-8 and (E)-8). In agreement with quantum calculations, 12 is unreactive toward SO(2) (no cycloaddition, only polymerization), whereas (E)-1-fluoro-1,3-dienes react more rapidly than their (Z)-isomers to give the corresponding 6-fluorosultines following the endo (Alder rule) mode of hetero-Diels-Alder addition. No sulfolene has been observed following the cheletropic mode of addition with the fluorodienes, in contrast to other substituted dienes. In agreement with the calculations, cis-2-fluoro-3,4-oxathiabenzobicyclo[4.4.0]dec-1(6),9-diene-4-oxide (cis-9, the sultine obtained by SO(2) addition to (Z)-8 under conditions of kinetic control) adopts a sofa conformation with the oxygen atom of the ring lying in the average plane of the four carbon atoms of its sultine moiety when it is in the crystalline state at -100 degrees C. A similar sofa conformation was found for its trans-isomer, trans-9, obtained by isomerization of cis-9 or by hetero-Diels-Alder addition of SO(2) to (E)-8. Experiments (equilibrium constant for hetero-Diels-Alder additions, bond lengths, and bond angles in crystalline fluorosultines cis-9 and trans-9) and high-level quantum calculations on cis- and trans-6-fluoro-3,6-dihydro-1,2-oxathiin-2-oxide (cis- and trans-20) confirm the existence of a stabilizing, enthalpic, anomeric (gem-disubstitution by sulfinyloxy and fluoro groups) effect, which is interpreted in terms of (lone pair) n(O1)-->sigma*(C-F) hyperconjugative interactions. This effect is strongest in the sofa conformers with a gauche arrangement of the sigma(O1,S2) and sigma(C6,F) bonds. The calculations suggest also that n(O1)-->sigma*(S2,O2'), pi*(S=O), and n(S2)-->sigma*(O1,C6) interactions intervene and affect the relative stability of the conformers (sofa, boat, pseudo-chair) found for 6-fluorosultines cis- and trans-20.
Roversi
Elena
E
Section de Chimie de l'Université, BCH, 1015 Lausanne-Dorigny, Switzerland.
Scopelliti
Rosario
R
Solari
Euro
E
Estoppey
Raphaël
R
Vogel
Pierre
P
Braña
Pedro
P
Menéndez
Bibiana
B
Sordo
José A
JA