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- Title
On the Mechanism of Internal ortho-Lithiation in a Mixed Complex Between BuLi and a Chiral Lithium Amide.
- Authors
Arvidsson, Per I.; Hilmersson, Göran; Davidsson, Öjvind
- Abstract
The chiral lithium amide Li- 1, prepared from ( S)- N-[( R)-2-methoxy-1-phenylethyl]- α-methylbenzylamine 1, is known to form a mixed complex with BuLi, i.e., Li- 1/BuLi. When this complex is kept at room temperature for 3-5 h, a regioselective lithiation of one of the ortho-C-atoms in the amide occurs. Kinetic studies indicate that this reaction proceeds within the mixed aggregate with a first-order rate constant for the rate-limiting step k2=9.4×10−4 s−1 (Δ G=21 kcal mol−1). Molecular modeling (semi-empirical PM3) suggests that the observed selectivity and reactivity are a consequence of the solvation and structure of the mixed complex, i.e., an example of a complex induced proximity effect (CIPE).
- Publication
Helvetica Chimica Acta, 2002, Vol 85, Issue 11, p3814
- ISSN
0018-019X
- Publication type
Article
- DOI
10.1002/1522-2675(200211)85:11<3814::AID-HLCA3814>3.0.CO;2-O