A formal synthesis of the C1-C9 fragment of amphidinolide C employing the Tamaru reaction.
Homoallylation of aldehydes with isoprene and triethylborane catalyzed by Ni(acac)(2) gave hydroxyalkenes in good yield with excellent regio- and stereoselectivity. Cross metathesis of the hydroxyalkenes with methyl acrylate using second-generation Grubbs catalyst and copper(I) iodide afforded alpha,beta-unsaturated esters, which underwent cyclization in the presence of DBU to produce tetrahydrofurans with the correct relative configuration for the C1-C9 fragment of amphidinolides C, C2, and F.
Paudyal
Mahesh P
MP
Department of Chemistry and Biochemistry, University of Missouri-St. Louis, One University Boulevard, St. Louis, Missouri 63121, USA.
Rath
Nigam P
NP
Spilling
Christopher D
CD
D000447:Aldehydes / Q000737:chemistry; D001880:Boranes / Q000737:chemistry; D002070:Butadienes / Q000737:chemistry; D002384:Catalysis; D045782:Hemiterpenes / Q000737:chemistry; D018942:Macrolides / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D009532:Nickel / Q000737:chemistry; D009942:Organometallic Compounds / Q000737:chemistry; D010420:Pentanes / Q000737:chemistry; D013237:Stereoisomerism; D000097442:Amphidinolides
D000447:Aldehydes; D001880:Boranes; D002070:Butadienes; D045782:Hemiterpenes; D018942:Macrolides; D009532:Nickel; D009942:Organometallic Compounds; D010420:Pentanes; C429132:amphidinolide C; D000097442:Amphidinolides; C005059:isoprene; C079756:triethylborane