The thiopyran route to polypropionates : sequential enantiotopic group selective enolization of meso 1,9-diketones

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Date
2007Author
Gillis, Harold Martin
Type
ThesisDegree Level
DoctoralMetadata
Show full item recordAbstract
Meso 1,9-diketones (six to seven stereocenters)are readily obtained by stepwise or simultaneous two-directional aldol reactions of tetrahydro-4H-thiopyran-4-one with a thiopyran-derived aldehyde. Enantioselective enolizations of these diketones with the lithium amide from (R,R)-bis(1-phenylethyl)amine occur with simultaneous kinetic resolution to give the mono-TMS enol ethers in >90% yields based on recovered starting material (BORSM) and >90% ee. The developed methodology was applied in synthetic studies towards the asymmetric synthesis of denticulatin A.
Degree
Doctor of Philosophy (Ph.D.)Department
ChemistryProgram
ChemistrySupervisor
Ward, Dale E.Committee
Attah-Poku, Sam; Palmer, David; Majewski, Marek; Kerr, Michael A.; Baranski, Andrzej S.Copyright Date
2007Subject
desymmetrization
denticulatin
chiral lithium amide