Catalyst-directed diastereoselectivity in hydrogenative couplings of acetylene to alpha-chiral aldehydes: formal synthesis of all eight L-hexoses.
Hydrogenative coupling of acetylene to alpha-chiral aldehydes 1a-4a using enantiomeric rhodium catalysts ligated by (S)-MeO-BIPHEP and (R)-MeO-BIPHEP delivers the diastereomeric products of carbonyl-(Z)-butadienylation 1b-4b and 1c-4c, respectively, with good to excellent levels of catalyst directed diastereofacial selectivity. Diastereomeric L-glyceraldehyde acetonide adducts 1b and 1c were converted to the four isomeric enoates 6b, 8b, 6c, and 8c, representing a formal synthesis of all eight L-hexoses.
Han
Soo Bong
SB
University of Texas at Austin, Department of Chemistry and Biochemistry, Austin, Texas 78712, USA.
Kong
Jong Rock
JR
Krische
Michael J
MJ
D000114:Acetylene / Q000737:chemistry*; D000447:Aldehydes / Q000737:chemistry*; D002384:Catalysis; D006601:Hexoses / Q000138:chemical synthesis* / Q000737:chemistry; D006859:Hydrogen / Q000737:chemistry*; D013237:Stereoisomerism; D013379:Substrate Specificity
D000447:Aldehydes; D006601:Hexoses; D006859:Hydrogen; D000114:Acetylene