Other Alkylations, Arylations, and Allylations of Imines

Nitrile-stabilized anions, generated for example by lithiation of benzyl cyanide and propionitrile, have been added diastereoselectively to aromatic aldimines.50 Acid workup gives /5-cyano amines. Alternatively, addition of RX gives /3-R-substituted-/3-cyanoamines. The factors determining des in both reaction versions have been investigated. 

Recent advances in asymmetric additions of dialkyl reagents to imines have been reviewed.51 

Arylboronic acids have been added diastereo- and enantio-selectively to (a) sulflnyl aldimines and (b) phosphinoyl aldimines, using rhodium(I) catalysts.52 These two methods should prove useful in preparing a-branched amines. 

A-Tosyl aldimines, RCH=N-Ts, add regioselectively to the C(2) of pyrroles, to give pyrrole sulfonamides (11), using copper(II) triflate as catalyst.53 

Anisidine imines of aldehydes, p-McOCfJ I4-N=CI IR (R = Ar, alkyl) can be ally-lated with anti-selectivity, using triethylborane and a Pd(II)-phosphine catalytic system, avoiding metallic or metalloid allylating agents 54 The imines can be conveniently formed in situ. 

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