TY - JOUR
T1 - Diels-Alder Reactions of S-Vinyl-S-Arylsulfoximines
AU - Glass, Richard S.
AU - Reineke, Karl
AU - Shanklin, Michael
PY - 1984/9
Y1 - 1984/9
N2 - Cyclopentadiene and the known S-p-tolyl-S-vinyl-A-phthalimidosulfoximine (1a) undergo Diels-Alder reaction to give a mixture of cycloadducts in excellent yield. The structures of the cycloadducts including stereochemistry are assigned by 1 H NMR spectroscopy. The crystal and molecular structure of the major cycloadduct 5d, n = 1, G = 1,2-C6 H4(CO)2 N was determined unequivocally by X-ray crystallographic techniques. Treatment of this major cycloadduct with hydrazine in ethanol resulted in conversion of the sulfoximine to sulfoxide group concomitant with reduction of the carbon-carbon double bond. Use of allyl alcohol as solvent in this reaction allowed conversion to the corresponding unsaturated sulfoxide 8. The previously unknown S-p-tolyl-S-vinyl-N-(p-tolylsulfonyl)-sulfoximine (1b) is somewhat more reactive than phenyl vinyl sulfone and undergoes Diels-Alder reactions with cyclic and acyclic 1,3-dienes in 81-95% yield. The endo selectivity of vinylsulfoximine 1b is 9:2 with cyclopentadiene and 93:7 with 1,3-cyclohexadiene. With 2-methyl-1,3-butadiene the para adduct is produced regioselectively in a ratio of 4:1. Although formation of the endo adducts from vinylsulfoximine 1b and “cyclopentadiene and 1,3-cyclohexadiene is not diastereoselective, the diastereomers can be separated by HPLC. The cycloadducts from 1,3-cyclohexadiene and vinylsulfoximine 1b have been converted to bicyclo[2.2.2]oct-2-ene and bicyclo-[2.2.2]oct-2-en-5-one.
AB - Cyclopentadiene and the known S-p-tolyl-S-vinyl-A-phthalimidosulfoximine (1a) undergo Diels-Alder reaction to give a mixture of cycloadducts in excellent yield. The structures of the cycloadducts including stereochemistry are assigned by 1 H NMR spectroscopy. The crystal and molecular structure of the major cycloadduct 5d, n = 1, G = 1,2-C6 H4(CO)2 N was determined unequivocally by X-ray crystallographic techniques. Treatment of this major cycloadduct with hydrazine in ethanol resulted in conversion of the sulfoximine to sulfoxide group concomitant with reduction of the carbon-carbon double bond. Use of allyl alcohol as solvent in this reaction allowed conversion to the corresponding unsaturated sulfoxide 8. The previously unknown S-p-tolyl-S-vinyl-N-(p-tolylsulfonyl)-sulfoximine (1b) is somewhat more reactive than phenyl vinyl sulfone and undergoes Diels-Alder reactions with cyclic and acyclic 1,3-dienes in 81-95% yield. The endo selectivity of vinylsulfoximine 1b is 9:2 with cyclopentadiene and 93:7 with 1,3-cyclohexadiene. With 2-methyl-1,3-butadiene the para adduct is produced regioselectively in a ratio of 4:1. Although formation of the endo adducts from vinylsulfoximine 1b and “cyclopentadiene and 1,3-cyclohexadiene is not diastereoselective, the diastereomers can be separated by HPLC. The cycloadducts from 1,3-cyclohexadiene and vinylsulfoximine 1b have been converted to bicyclo[2.2.2]oct-2-ene and bicyclo-[2.2.2]oct-2-en-5-one.
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U2 - 10.1021/jo00183a010
DO - 10.1021/jo00183a010
M3 - Article
AN - SCOPUS:0001627397
SN - 0022-3263
VL - 49
SP - 1527
EP - 1533
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
IS - 9
ER -