Journal of Organic Chemistry p. 5963 - 5967 (1989)
Update date:2022-08-04
Topics:
Juaristi, Eusebio
Gordillo, Barbara
Martinez, Roberto
Toscano, Ruben A.
A single-crystal X-ray structure determination of the title sulfoxide (cis-2) was carried out and compared with data previously reported for the corresponding sulfone (cis-1).Whereas the latter adopts an eclipsed conformation (one S-C/C-H and two S=O/C-C eclipsed bond pairs), both the tert-butyl and the S=O group in the sulfinyl function point outside the ring in a staggered rotamer.A substantial difference in length for the endocyclic C-C bonds in cis-2 suggests the effect of through-space ?C-C/?*S-O (attractive) and ?C-C/nS (repulsive) interactions and/or ?C-H -> ?*C-S stereoelectronic mechanisms.The X-ray diffraction study of the cyclohexane analogue (cis-4) shows again a staggered conformation for the tert-butylsulfinyl group, but confirms the repulsive steric hindrance between the gauche t-BuS and endocyclic methylene groups.The contrasting behavior between the sulfone and sulfoxide groups points to the existence of an attractive interaction S=O/C-C, which stabilizes the eclipsed conformer in cis-1 and overcomes the torsional strain in the eclipsed bond pair S-C/C-H.The nature of the stabilizing S=O/C-C interaction is proposed in the light of recent theoretical calculations.
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