A general stereocontrolled, convergent synthesis of oligoprenols that parallels the biosynthetic pathway.
A solution is reported to the classic unsolved problem of stereoselective synthesis of all-E oligoprenols, such as E-farnesylfarnesol, by a cationic coupling analogous to the biosynthetic pathway. The simplicity and efficacy of the method, which is outlined in Scheme 1, are demonstrated by the synthesis of a series of all-E oligoprenols from C(20) to C(35) in uniformly excellent overall yield. The success of the approach is due not only to the highly E-stereoselective C-C coupling that forms the oligoprenyl chain but also to the development of efficient syntheses of allylic secondary silanes and E-oligoprenal acetals, and to a selective allylic demethoxylation reaction.
Radetich
Branko
B
Department of Chemistry and Chemical Biology, Harvard University, Cambridge, MA 02138, USA.
Corey
E J
EJ
D000080462:Acyclic Monoterpenes; D004224:Diterpenes / Q000138:chemical synthesis / Q000378:metabolism; D005204:Farnesol / Q000138:chemical synthesis / Q000378:metabolism; D045782:Hemiterpenes; D000439:Pentanols / Q000138:chemical synthesis* / Q000378:metabolism; D013237:Stereoisomerism; D013729:Terpenes / Q000138:chemical synthesis* / Q000378:metabolism
D000080462:Acyclic Monoterpenes; D004224:Diterpenes; D045782:Hemiterpenes; D000439:Pentanols; D013729:Terpenes; D005204:Farnesol; C009034:prenol; C017338:geranylgeraniol; C017719:solanesol; C007836:geraniol