Synthesis of the C(1)-C(12) segment of peloruside A by an alpha-benzyloxymethyl ketone aldol strategy.
The C(1)-C(12) segment of 16-membered antitumor macrolide peloruside A has been prepared by a BF(3).OEt(2)-catalyzed Mukaiyama aldol reaction between a glucose-derived C(1)-C(7) aldehyde and a C(8)-C(12) alpha-benzyloxymethyl ketone. Exclusive 2,3-anti and moderate 3,5-anti/syn facial selectivity (3.5:1) was observed in the aldol reaction. The key C(1)-C(7) aldehyde contains the required stereochemistry at carbons two, three, and five, and has been efficiently prepared on multigram scales from commercial triacetyl D-glucal. [reaction: see text]
Engers
Darren W
DW
Department of Chemistry and Biochemistry, The University of Texas at Austin, Austin, TX 78712, USA.
Bassindale
Martin J
MJ
Pagenkopf
Brian L
BL
D000447:Aldehydes / Q000737:chemistry; D000818:Animals; D000970:Antineoplastic Agents / Q000138:chemical synthesis*; D019086:Bridged Bicyclo Compounds, Heterocyclic / Q000138:chemical synthesis*; D002384:Catalysis; D007659:Ketones / Q000737:chemistry; D007783:Lactones / Q000138:chemical synthesis*; D018942:Macrolides / Q000138:chemical synthesis; D015394:Molecular Structure; D011161:Porifera; D013237:Stereoisomerism
D000447:Aldehydes; D000970:Antineoplastic Agents; D019086:Bridged Bicyclo Compounds, Heterocyclic; D007659:Ketones; D007783:Lactones; D018942:Macrolides; C414085:peloruside A