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17 O NMR Spectroscopy of Sulfolenes (2, 5‐Dihydrothiophene‐1,1‐dioxides) and Sultines (3, 6‐Dihydro‐1,2‐oxathiin‐2‐oxides)‐Experiment and Quantum Calculations: Synthesis of 4, 9‐Dioxo‐1,2‐oxathiacyclodecane‐2‐oxide, a New Heterocycle
Author(s) -
Roversi Elena,
Monnat Frédéric,
Schenk Kurt,
Vogel Pierre,
Braña Pedro,
Sordo José A.
Publication year - 2000
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/(sici)1521-3765(20000515)6:10<1858::aid-chem1858>3.0.co;2-u
Subject(s) - chemistry , adduct , ozonolysis , nuclear magnetic resonance spectroscopy , reactivity (psychology) , medicinal chemistry , computational chemistry , stereochemistry , organic chemistry , medicine , alternative medicine , pathology
The products of hetero‐Diels‐Alder reactions (sultines) and cheletropic addition reactions (sulfolenes) between 1,3‐dienes and sulfur dioxide can be distinguished by their 17 O NMR shifts. Experimental data have been collected for derivatives of 3,6‐dihydro‐1,2‐oxathiin‐2‐oxide and of 2,5‐dihydrothiophene‐1,1‐dioxide. This data was then compared with that calculated by the gauge independent atomic orbital (GIAO) method at the HF/6–31+G(d,p) and HF/6–311+G(3df, 2p) levels of theory with geometries optimized by MP2/6–31G(d) calculations. GIAO‐MBPT(2) calculations were also performed with the 6–31+G(d,p) basis set. The adduct between ( E )‐1‐methoxybutadiene and SO 2 is sulfolene 3 , the ozonolysis of which in SO 2 followed by work‐up with ethanol provided (2 RS ,3 SR ,6 SR )‐( 31 ), (2 RS ,3 RS ,6 SR )‐( 32 ), and (2 RS ,3 RS , 6 RS )‐2,6‐diethoxy‐3‐methoxy‐1,4‐oxathiane‐4,4‐dioxide ( 33 ). Single‐crystal X‐ray diffraction studies are reported for 32 and 33 . Ozonolysis of the hetero‐Diels‐Alder adduct of SO 2 with 1,2‐dimethylidenecyclohexane produced 4,9‐dioxo‐1,2‐oxathiacyclodecane‐2‐oxide ( 34 ), the first member of a new class of sulfur heterocycles.