Direct Substitution Reaction Of Allylic Amines Under Palladium Catalysis

Primary allylic amines are purified easily. The by-product of the allylic substitution is ammonia, so the reaction has better atom economy. Additionaly, chiral allylic amine can be resolved by (-)-tartaric acid in lage amounts. Allylic amine is seldom used in allylic substitution reaction because its amino group is dfficult to leave away. We find palladium/acid is able to catalyze the allylic substitution reactions of primary allylic amines.Secondary or tertiary allylic amines can be synthesized by means of deammoniative condensation of the primary allylic amines with nonallylic amines under Pd(OAc)2/TsOH catalysis. When primary a-branched chiral allylic amines are used as substrates, chiral allylic amines can be synthesized in a chiral transfer manner. This is the first report accounts for the amine exchange reactions between primary allylic amines and nonallylic amines and have better yield than earlier reports.Chiral N-allylic hydrazines are widely used in organic synthesis. But most of earlier literatures are account for synthsis chiral symmetrical (a-substituent=y-substituent) allylic N-Allylhydrazines. Chiral unsymmetrical N-Allylhydrazines can be synthesized by deammoniative condensation of chiral primary allylic amines with nonallylic amines in a stereospecific manner under Pd(OAc)2/TsOH catalysis. N-allylhydrazine can be used to synthesize chiral functionalized tetrahydropyrazole.Racemic primary allylic amines can be resolved by asymmetric allylic alkylation of malononitriles with the help of mesitylsulfonyl hydrazide under palladium catalysis. The reaction has excellent regioseletivity and can be used as a good method to synthesize enatioenriched primary allylic amines and allyl-substituted malononitriles. This is the first example accounts for kinetic resolution of primary allylic amines via C-N bond cleavage and has better resolution result than earlier reports(s up to491).