IMDA/aldol strategy for transforming carbohydrates into functionalized trans-decalins.
L-Rhamnal is readily converted into an allyl 2, 3-unsaturated-C-glycopyranoside. The (S) configuration of the alphaL-anomer defines the stereochemical outcome of the future IMDA reaction, leading to the absolute stereochemistry for the trans-decalin moiety in naturally occurring terpenoids. Selective cleavage of the terminal double bond of the allyl group provides an aldehydo function which serves for an aldol/Claisen addition with ethyl sorbate. Of the four possible diastereomers, one is obtained in pure form and processed to give the IMDA precursor. Cyclocondensation is achieved by heating in xylene to give a tricyclic trans-decalin whose structure is established by NMR and X-ray analysis.
Fraser-Reid
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Natural Products and Glycotechnology Research Institute, Inc., Durham, North Carolina. Dglucose@aol.com
Chen
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Haag
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Henry
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McPhail
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D002241:Carbohydrates / Q000737:chemistry*; D002621:Chemistry / Q000379:methods*; D018360:Crystallography, X-Ray; D006027:Glycosides / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D008956:Models, Chemical; D008958:Models, Molecular; D008968:Molecular Conformation; D009281:Naphthalenes / Q000737:chemistry*; D013237:Stereoisomerism; D013729:Terpenes / Q000737:chemistry; D014965:X-Rays
D002241:Carbohydrates; D006027:Glycosides; D009281:Naphthalenes; D013729:Terpenes; C007229:decalin