Enantioselective Alkylations and Additions of Other C -nucleophiles to Imines

Enantioselective Alkylations and Additions of Other C-nucleophiles to Imines 

Enantioselective addition of C-nucleophiles to imines and hydrazones has been reviewed (1998-2009) another review describes the synthesis of a-branched amines by nucleophilic addition of unstabilized carbanions, including application in stereoselective reactions.  

Imine reactions catalysed by BlNOL-phosphoric acids have been modelled, using DFT calculations the model can predict the correct enantioselectivity for a wide range of reactions in the literature, based on the E/Z preference of the transition state, and the catalyst-nucleophile orientation.  

Monofluorobenzyl carbanions can be stabilized by an ort/io-sulfinyl group (35), which, if homochiral, reacts with A-p-tolylsulfinylimines (36) with complete stereoselectivity. The sulfinyl auxiliaries can then be removed with t-butyllithium without benzylic epimerization, giving enantiopure /3-fluoro- 3-phenethylamines (37). (S) 

A short review examines nucleophilic trifluoromethylation of C=N bonds imines, hydrazones, and nitrones, together with iminium cations and azomethine imines, mainly focusing on the Ruppert-Prakash reagent, TMS-CF3.  

---