Abstract
The isomerization of a variety of allylic alcohols with formation of the corresponding
saturated carbonyl compounds is readily accomplished by a new catalyst system comprising
rhodium and a trisubstituted phosphinine (phosphabenzene derivative), especially when
the Rh complex is activated by hydrogen prior to the transposition reaction.
Key words
green chemistry - homogeneous catalysis - isomerization - phosphorus - rhodium
References and Notes
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General Procedure for the Isomerization of Allylic Alcohol.
A dry 5-mL Schlenk flask under an atmosphere of argon was charged with a 5.4 mM solution
of P-ligand (0.5 mL) in dry CH2Cl2 and a 5.4 mM solution of [Rh(NBD)2]BF4 (0.25 mL) in CH2Cl2. The mixture was stirred for 30 min at r.t., then stirred for an additional 30 min
under 1.3 bar H2. The CH2Cl2 and H2 were removed by Ar displacement under reduced pressure, then 0.5 mL of CH2Cl2 and a 67.5 mM solution of an allylic alcohol in CH2Cl2 (1 mL) were added. The isomerization was carried out for the periods given. The reaction
solution was passed through a small amount of silica gel and selectivity and conversion
were determined by gas chromatography (GC and GC-MS).