Asymmetric synthesis of 1,2-dioxolane-3-acetic acids: synthesis and configurational assignment of plakinic acid A.
The first asymmetric synthesis of 1,2-dioxolane-3-acetic acids is reported. Key features include the stereoselective opening of enantiomerically enriched oxetanes by hydrogen peroxide, conversion of the resulting 4-hydroperoxy-2-alkanols to 3-alkoxy-1,2-dioxolanes, and Lewis acid mediated homologation of the latter with a thioester silyl ketene acetal. The approach is modeled on 3,5-dimethyl-5-hexadecyl-1,2-dioxolane-3-acetic acid (1a), an unnamed natural product, and an optimized strategy is applied to the synthesis of four stereoisomers of plakinic acid A (2), allowing a configurational assignment of this incompletely characterized natural product.
Dai
Peng
P
Department of Chemistry, University of Nebraska-Lincoln, Lincoln, Nebraska 68588-0304, USA.
Trullinger
Tony K
TK
Liu
Xuejun
X
Dussault
Patrick H
PH
D000438:Alcohols / Q000737:chemistry*; D004148:Dioxolanes / Q000138:chemical synthesis* / Q000737:chemistry; D008968:Molecular Conformation; D013237:Stereoisomerism
D000438:Alcohols; D004148:Dioxolanes; C516353:plakinic acid A