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Original Articles

STEREOCHEMISTRY OF THE ADDITION OF α-METALLATED N,N-DIALKYLSULFONAMIDES TO ALDEHYDES

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Pages 155-165 | Received 18 Oct 1988, Published online: 04 Oct 2006

References

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  • This observation, as well as the relatively moderate values of δv oh, 54 to 75 cm−1 for the erythro, and 93 to 113 cm−1 for the threo isomers, indicates that this conformation is favoured by the polar interaction of the hydroxyl oxygen and the positively charged sulfur of the sulfonyl group11rather than by hydrogen bonding. The same conformations are favoured also in β-hydroxysulfonamides4,6 and β-hydroxysulfones.10
  • Mladenova , M. , Blagoev , B. and Kurtev , B. 1979 . Bull. Soc. Chim. Fr. , : 11 – 77 . but gives the threo isomer under thermodynamic control, Such cases are by no means rare. For example, the addition of N,N-dimethylphenylacetamide carbanion to benzaldehyde is nonstereoselective under kinetic control
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  • Stefanovsky , J. N. and Grancarova , N. 1968 . Compt. rend. Acad. bulg. Sci. , 21 : 249 The lithiated N,N,N′,N′-tetramethylamide of phenylmethanephosphonic acid adds to benzaldehyde nonstereoselectively at -70°C, but at ambient temperature gives only the thermodynamically more stable erythro isomer
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  • Goasdoue , C. , Goasdoue , N. , Gaudemar , M. and Mladenova , M. 1981 . J. Organometal. Chem. , 208 : 279 An example is the addition of R1CH(Li)CSN(CH3),2 to benzaldehyde under kinetic control, -20°C, THF. Substituent effects on product stereochemistry are markedly stronger; for R1 = CH,3, erythro: threo = 63:37, for R1 = C6H5 - 22:78, and for R1 = i-Pr only the threo isomer is obtained. For R1 = CH3 and pivalaldehyde the steric interaction of t-Bu and N(CH3)2 leads in turn to the pure erythro isomer
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