Stereoselective olefin isomerization leading to asymmetric quaternary carbon construction.
Chemo- and stereoselective Ir(I)-catalyzed isomerization of 1,1-disubstituted and trisubstituted allylic ethers and in situ [3,3] sigmatropic rearrangement of the resulting allyl vinyl ethers provide for the highly stereoselective construction of quaternary carbon stereocenters. The olefin isomerization-Claisen rearrangement (ICR) sequence allows adjacent quaternary-tertiary stereocenter relationships to be established with excellent diastereoselection. Several complementary strategies for enantioselective quaternary carbon synthesis derive directly from the ICR reaction design.
Wang
Kan
K
Department of Chemistry, University of Pittsburgh, Pittsburgh, Pennsylvania 15260, USA.
Bungard
Christopher J
CJ
Nelson
Scott G
SG
D000475:Alkenes / Q000138:chemical synthesis / Q000737:chemistry*; D008968:Molecular Conformation; D013237:Stereoisomerism
D000475:Alkenes