Dihydrothiophenes containing quaternary stereogenic centres by sequential stereospecific rearrangements and ring-closing metathesis.
Stereospecific [3,3]-sigmatropic rearrangement of O-substituted thiocarbamate derivatives of enantiopure allylic alcohols provides allylic thiocarbamates as single enantiomers. Intramolecular arylation by rearrangement of their allyllithium derivatives provides allylic tertiary thiols. Allylation and ring-closing metathesis gives 2,5-dihydrothiophenes containing sulfur-bearing quaternary centres.
School of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL, UK. clayden@man.ac.uk.
Gaëlle
G
Mingat
Joseph J W
JJ
McDouall
Jonathan
J
Clayden
D000438:Alcohols / Q000737:chemistry; D000498:Allyl Compounds / Q000737:chemistry; D002942:Circular Dichroism; D007202:Indicators and Reagents; D008968:Molecular Conformation; D013237:Stereoisomerism; D013455:Sulfur / Q000737:chemistry; D013859:Thiocarbamates / Q000737:chemistry; D013876:Thiophenes / Q000737:chemistry*
D000438:Alcohols; D000498:Allyl Compounds; D007202:Indicators and Reagents; D013859:Thiocarbamates; D013876:Thiophenes; D013455:Sulfur