Reactivity of Trogers Bases

The reactivity of TBs will be divided in three sections classical, chiral resolution and organometallic complexes. 

The acetylation, benzoylation and nitrosilation of 1 were performed by Spielman in his original determination of the structure of TB 1 (35JA583). Reaction with acetic anhydride or benzoyl chloride yielded the diacetyl 77a and dibenzoyl 77b derivatives, respectively. Note that these reactions involved the loss of one carbon atom as 

The dinitroso derivative 77c was converted into the amine 12b in high yield upon treatment with CuCl/HCl (57JCS2888). Metallation of 1 with -BuLi in the presence of boron trifluoride etherate afforded an organolithium TB functionalized at a benzylic methylene position. Subsequent reaction with electrophiles furnished alkylation products 78 without loss of stereochemical integrity (96TL6267, 00TA2875). 

Chiral Resolution and Optical Properties of Troger s Bases 

An enantioselective dynamic electrokinetic chromatography technique was used by Trapp et al. for determination of rate constants, enantiomerization barriers (AG (298 K) = 100.9 + 0.5 kJ mol ) and activation parameters [AH (298K) = 89.5+ 2.0 kJ mol AS (298K) = -42+10J mol 1 K ] of 1 at pH 2.2 (02CEJ3629). Introduction of a permanent positive charge in TB 1 significantly decreased the enantiomerization, which is not in conflict with the iminium-based theory. 

---