Organoiithium reagents, with

The highly selective asymmetric addition of organolithiums to acyclic imines and N-aryl group oxidative removal provided a facile and efficient synthetic route to the optically active 1-substituted tetrahydroisoquinoline (TIQ) 81 [74] (Scheme 24), (R)-(-i-)-salsohdine (84) [71] (Scheme 25), and optically pure a-amino acid derivatives 88 bearing a bulky a-substituent [75] (Scheme 26). The reaction of organoiithium reagents with the acyclic imine 78 and subsequent cy-clization of the secondary amine under Moffat oxidation conditions, after oxidative hydroboration of 79, gave 80 (Scheme 24). 

A. Epoxide Ring Opening with Nonstabilized Organoiithium Reagents. . 1195... 

The BHA group exerts remarkable activating and directing effects on the reaction of naphthalenecarboxylates with organoiithium reagents [24,25]. In the presence of either stoichiometric or catalytic amounts of the chiral diether 18, aryllithiums reacted with BHA esters of 1- and 2-naphthalenecarboxylic acid 21/22 to afford 1,2-di-, 1,1,2- and 1,2,2-trisubstituted dihydronaphthalenes 23/24 in high ee, following a subsequent ketene-reduction in a one-pot process (Scheme 7). 

The (S)-proline-derived chiral ligand 104, similar to the aminoether 15, mediates the asymmetric addition of organoiithium reagents to arylimines 103 producing (S)-amine 105 with relatively poor enantiomeric excess, up to 21 % ee (Scheme 31) [84-86]. 

Reactions with Organoiithium Compounds, Grignard Reagents, and Other Organoeiement Compounds... 

Organoiithium compounds react with esters, acid chiorides, and anhydrides in the same way as Grignard reagents. Reaction with carboxyiic acids gives ketones, but 2 moi of organoiithium are required. 

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