Studies of alpha-lithioamine synthetic equivalents: I. Elaboration of primary amines. II. Detection of an intermediate in the lithiation of a benzylic urea
Reagents for the $\alpha$-substitution of N-Boc-benzylamine and N-Boc-allylamine have been developed via dilithiation and electrophilic substitution. Discussion of the specific conditions employed to accomplish these transformations is presented, as well as mechanistic speculation. Dilithiation and substitution of O-benzyl-N-methyl carbamate has been achieved, and use of sec-BuLi/(-)sparteine as the base provided the corresponding products with up to 57% enantiomeric excess. Lithiation of N-tert-butyl-N-benzyl carbamates resulted in rearrangement to phenylglycine derivatives. These related investigations are also discussed.
University of Illinois - Urbana-Champaign
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University of Illinois at Urbana-Champaign