Allylamines anti selectivity

The most frequently used metallic catalysts for acyldiazo- and (alkoxycarbonyl)dia-zomethanes are complexes or salts of rhodium, palladium and copper. Alkenylboronic esters A-silylated allylamines and acetylenes are successfully cyclopropanat-ed with diazocarbonyl compounds under catalysis of one of those metal derivatives. Newly developed metallic catalysts for diazoacetic esters include polymer-bound, quantitatively recoverable Rh(II) carboxylate salts ", Cu(II) supported on NATION ion exchange poly-mer ruthenacarborane clusters, Rh2(NHCOCH3)4 which produces cyclopropanes with substantially enhanced trans (anti) selectivity as shown below and (rj -CsHs)... 

Chiral racemic vinylepoxides react with phthalimide at the more substituted end of the 7t-allyl intermediate to give the chiral allylamine in up to 98% ee. Scheme 34 [ 116]. Some modification of the standard DPPBA-type ligand was required in order to achieve this level of selectivity. In particular, increased steric bulk in the form of a naphthyl moiety was claimed to restrict the number of ro-tamers and thereby increase the selectivity. This sequence was used to prepare vinylglycinol and a related reaction was used to synthesize a key intermediate for the synthesis of some anti-fungal agents [117]. 

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