Highly selective 1,3-isomerization of allylic alcohols via rhenium oxo catalysis.
Two reaction strategies are developed to promote the highly selective 1,3-isomerization of a variety of allylic alcohols using O3ReOSiPh3 as a catalyst. The first strategy utilizes substrates whose 1,3-regioisomer contains a conjugated alkene, which relies on thermodynamics to obtain high selectivity. The second strategy employs N,O-bis(trimethylsilyl)acetamide as an additive to selectively and irreversibly remove the product from the reaction equilibrium and works well for the isomerization of tertiary allylic alcohols into primary allylic alcohols containing trisubstituted alkene components. High stereoselectivity is also observed in the 1,3-isomerization of enantioenriched allylic alcohols.
Morrill
Christie
C
Arnold and Mabel Beckman Laboratory of Chemical Synthesis, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, USA.
Grubbs
Robert H
RH
D000438:Alcohols / Q000737:chemistry*; D000498:Allyl Compounds / Q000737:chemistry*; D002384:Catalysis; D007536:Isomerism; D012211:Rhenium / Q000737:chemistry*
D000438:Alcohols; D000498:Allyl Compounds; D012211:Rhenium