793726-45-1Relevant articles and documents
Iridium-catalyzed, asymmetric amination of allylic alcohols activated by lewis acids
Yamashita, Yasuhiro,Gopalarathnam, Apsara,Hartwig, John F.
, p. 7508 - 7509 (2008/02/11)
The direct, Ir-catalyzed, regio- and enantioselective amination of allylic alcohols with Lewis acid activators to form branched allylic amine products is reported. The reactions of arylamines, benzylic amines, and secondary aliphatic amines in the presence of Nb(OEt)5 as activator occurred with high regioselectivities and high enantioselectivities. These results led to the development of Ir-catalyzed reactions of allylic alcohol with arylamines and BPh3 as activator in catalytic amounts. These reactions are rare examples of enantioselective substitutions of allylic alcohols. They are particularly unusual examples of the substitution of allylic alcohols to generate branched substitution products from monosubstituted allylic alcohols and of enantioselective substitutions of allylic alcohols with amine nucleophiles. Copyright
Enantioselective allylation of aromatic amines after in situ generation of an activated cyclometalated iridium catalyst
Shu, Chutian,Leitner, Andreas,Hartwig, John F.
, p. 4797 - 4800 (2007/10/03)
Highly regio- and enantioselective allylation of aromatic amines is observed when a cyclometalated Ir-phosphoramidite complex is generated in situ (see scheme). The active catalyst can be formed from [{Ir(cod)Cl}2] and ligand L with a volatile alkylamine prior to addition of the reagents or upon use of a tertiary amine additive.
ENANTIOSELECTIVE AMINATION AND ETHERIFICATION___________________
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Page 20; 45, (2010/02/06)
The present invention is directed to a catalyst composition, comprising: (1) a catalyst precursor having the general structure MSXn wherein M is a transition metal selected from the group consisting of iridium, molybdenum, and tungsten; S is a coordinating ligand; X is a counterion; and n is an integer from 0 to 5; and (2) a phosphoramidite ligand having the structure wherein O-Cn-O is an aliphatic or aromatic diolate and wherein R1, R2, R3 and R4 are selected from the group consisting of substituted or unsubstituted aryl groups, substituted or unsubstituted heteroaryl groups, substituted or unsubstituted aliphatic groups, and combinations thereof, with the proviso that at least one of R1, R2, R3, or R4 must be a substituted or unsubstituted aryl or heteroaryl group. The present invention is also directed to activated catalysts made from the above catalyst composition, as well as methods of allylic amination and etherification using the above catalysts.
Palladium(0)-Catalyzed Allylation of Highly Acidic and Nonnucleophilic Anilines. the Origin of Stereochemical Scrambling When Using Allylic Carbonates
Moreno-Manas, Marcial,Morral, Lurdes,Pleixats, Roser
, p. 6160 - 6166 (2007/10/03)
Acidic anilines such as diphenylamine, phenothiazine, and nitroanilines are efficiently allylated under palladium catalysis using allyl carbonates as allylating reagents. A stereochemical study of the reactions of ethyl cis-5-methyl-2-cyclohexenylcarbonate with 4-nitro- and 2,4-dinitroaniline was performed. Bidentate phosphines as stabilizing ligands gave clean retention of configuration whereas triphenylphosphine permitted cis-trans isomerization of the allylic carbonate, the allylation reactions occurring under Curtin-Hammet preequilibrium conditions.
