Allylic amine isomerization rhodium-catalyzed

In the Rh-BINAP-catalyzed allyl amine isomerization step used in Takasago s Menthol process, the catalyst is inhibited by water through the formation of a hydroxyl-bridged rhodium trinuclear complex [ Rh(BINAP) i(/<2-0H)2]C104 [61]. 

Allylic amide isomerization, 117 Allylic amine isomerization ab initio calculations, 110 catalytic cycle, 104 cobalt-catalyzed, 98 double-bond migration, 104 isotope-labeling experiments, 103 kinetics, 103 mechanism, 103 model system, 110 NMR study, 104 rhodium-catalyzed, 9, 98 Allylnickel halides, 170 Allylpalladium intermediates, 193 Allylsilane protodesilylation, 305 Aluminum, chiral catalysts, 216, 234, 310 Amide dimers, NMR spectra, 282, 284 Amines ... 

RHODIUM-CATALYZED ENANTIOSELECTIVE ISOMERIZATION OF ALLYLIC AMINES... 

RHODIUM-CATALYZED enantioselective isomerization of ALLYLIC AMINES 103... 

There are several relevant aspects of rhodium enolate chemistry. Rh(I) catalyzes the isomerization of allylic aUtoxides to enolates. We welcome this reaction done in a direct thermochemical context analogous to the related isomerizations of allyl halides , ethers and allyl amines . From the enthalpies of formation of allyl alcohol and propanal (—185.6 and —124.5 kJmol ), and their respective gas phase deprotonation enthalpies (1564 and 1530 kJ mol 252,253 jj. jjg concluded that the rearrangement of the allyloxide to propen-1-olate is exothermic by 95 kJmoR. ... 

Rhodium(I)-catalyzed isomerization of allylic amines is also good route to P-substituted aldehydes [89]. 

RHODIUM-CATALYZED ENANTlOSri fCTIVE ISOMERIZATION OF ALLYLIC AMINES 101... 

RHODIUM-CATALYZED ENANTIOSELFCTIVE ISOMERIZATION OF ALLYLIC AMINES 115... 

When either an alcohol or an amine function is present in the alkene, the possibility for lactone or lactam formation exists. Cobalt or rhodium catalysts convert 2,2-dimethyl-3-buten-l-ol to 2,3,3-trimethyl- y-butyrolactone, with minor amounts of the 8-lactone being formed (equation 51).2 In this case, isomerization of the double bond is not possible. The reaction of allyl alcohols catalyzed by cobalt or rhodium is carried out under reaction conditions that are severe, so isomerization to propanal occurs rapidly. Running the reaction in acetonitrile provides a 60% yield of lactone, while a rhodium carbonyl catalyst in the presence of an amine gives butane-1,4-diol in 60-70% (equation 52).8 A mild method of converting allyl and homoallyl alcohols to lactones utilizes the palladium chloride/copper chloride catalyst system (Table 6).79,82 83... 

There are other Pd-catalyzed procedures for deallylation." Allyl groups attached directly to amine or amide nitrogen can be removed by isomerization and hydrolysis. Catalysts which have been found to be effective include Wilkinson s catalyst/ other rhodium catalysts, and iron pentacarbonyl. 2,2,2-Trichloroethylcarbamates can be reductively cleaved by zinc." ... 

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