title: Carboxylate-stabilised sulfur ylides (thetin salts) in asymmetric epoxidation for the synthesis of glycidic acids. Mechanism and implications.
abstract: The reaction of carboxylate-stabilised sulfur ylides (thetin salts) with aldehydes and ketones has been investigated. Using both achiral and chiral sulfur ylides, good yields were obtained with dimsylsodium or LHMDS as bases in DMSO or THF-DMSO mixtures. However, the enantioselectivities observed with a camphor-based sulfide were only moderate (up to 67%). The reaction was studied mechanistically by independent generation of the betaine (via the hydroxyl sulfonium salt) in the presence of a more reactive aldehyde, which resulted in incorporation of the more reactive aldehyde and showed that betaine formation was reversible. Thus, the moderate enantiomeric excess observed is a consequence of the enantiodifferentiating step being the ring closure step rather than the betaine forming step. We had expected betaine formation might be non-reversible because a carboxylate-stabilised ylide has only slightly higher stability than a phenyl-stabilised ylide, which does largely react non-reversibly with aldehydes. Evidently, a carboxylate-stabilised ylide is significantly more stable than a phenyl-stabilised ylide and as such reacts reversibly with aldehydes.
authors.affiliation: University of Bristol, Cantock's Close, UK. V.Aggarwal@Bristol.ac.uk
authors.forename: Varinder K
authors.initials: VK
authors.lastname: Aggarwal
authors.forename: Christina
authors.initials: C
authors.lastname: Hebach
mesh_terms: D000577:Amides / Q000737:chemistry; D001622:Betaine / Q000737:chemistry; D019086:Bridged Bicyclo Compounds, Heterocyclic / Q000737:chemistry*; D002264:Carboxylic Acids / Q000737:chemistry*; D018360:Crystallography, X-Ray; D004852:Epoxy Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D006900:Hydroxylation; D015394:Molecular Structure; D011422:Propionates / Q000138:chemical synthesis* / Q000737:chemistry; D012492:Salts / Q000737:chemistry*; D013237:Stereoisomerism; D013455:Sulfur / Q000737:chemistry*
chemical_list: D000577:Amides; D019086:Bridged Bicyclo Compounds, Heterocyclic; D002264:Carboxylic Acids; D004852:Epoxy Compounds; D011422:Propionates; D012492:Salts; D001622:Betaine; C007869:glycidic acid; D013455:Sulfur