Stereoselective synthesis of cyclic ethers via the palladium-catalyzed intramolecular addition of alcohols to phosphono allylic carbonates.
Cross metathesis of the acrolein-derived phosphono allylic carbonate and hydroxy alkenes using second generation Grubbs catalyst and copper(I) iodide gave the substituted phosphonates in good yield. Stereospecific palladium(0)-catalyzed cyclization gave tetrahydrofuran and tetrahydropyran vinyl phosphonates. Regioselective Wacker oxidation of the vinyl phosphonate gave the beta-keto phosphonate, which underwent HWE reaction with benzaldehyde to yield the unsaturated ketone. The utility of the cross metathesis/cyclization protocol was further demonstrated by a formal synthesis of centrolobine.
He
Anyu
A
Department of Chemistry and Biochemistry, University of Missouri-St. Louis, One University Boulevard, St. Louis, Missouri 63121, USA.
Sutivisedsak
Nongnuch
N
Spilling
Christopher D
CD
D000438:Alcohols / Q000737:chemistry*; D000475:Alkenes / Q000138:chemical synthesis* / Q000737:chemistry; D000498:Allyl Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D002254:Carbonates / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D003500:Cyclization; D004988:Ethers, Cyclic / Q000138:chemical synthesis* / Q000737:chemistry; D007659:Ketones; D015394:Molecular Structure; D009943:Organophosphorus Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D010165:Palladium; D013237:Stereoisomerism
D000438:Alcohols; D000475:Alkenes; D000498:Allyl Compounds; D002254:Carbonates; D004988:Ethers, Cyclic; D007659:Ketones; D009943:Organophosphorus Compounds; D010165:Palladium