Stereoselective synthesis of functionalized trisubstituted olefins via palladium(0)-catalyzed cross-coupling reaction.
[reaction: see text]. A highly flexible and stereoselective protocol for the synthesis of branched (E)- and (Z)-trisubstituted alkenes has been developed. The key steps are hydrozirconation-iodination of (1-alkynyl)trimethylsilane followed by Negishi-type cross-coupling. The resultant (Z)-vinyl silane is iododesilylated and subjected to a second cross-coupling reaction to give the trisubstituted olefin. Model studies aimed at the construction of the C14-C15 (Z)-trisubstituted olefin of discodermolide and the C8-C9 (Z)-trisubstituted olefin of callystatin A and analogues are also described.
Arefolov
A
A
Department of Chemistry and Center for Streamlined Synthesis, Metcalf Center for Science and Engineering, 590 Commonwealth Avenue, Boston University, Boston, Massachusetts 02215, USA.
Langille
N F
NF
Panek
J S
JS
D000473:Alkanes; D000475:Alkenes / Q000138:chemical synthesis*; D002219:Carbamates; D002384:Catalysis; D005231:Fatty Acids, Unsaturated / Q000138:chemical synthesis; D007455:Iodine; D007783:Lactones / Q000138:chemical synthesis; D008958:Models, Molecular; D010165:Palladium / Q000737:chemistry; D011753:Pyrones; D012821:Silanes; D013237:Stereoisomerism; D015040:Zirconium
D000473:Alkanes; D000475:Alkenes; D002219:Carbamates; D005231:Fatty Acids, Unsaturated; D007783:Lactones; D011753:Pyrones; D012821:Silanes; C421091:callystatin A; D010165:Palladium; D007455:Iodine; D015040:Zirconium; C071229:discodermolide