Four Enantiomerization Routes of 1,2,2-Trimesitylvinyl Acetate. Enantioselective Liquid Chromatography of (E)- and (Z)-2-m-Methoxymesityl-1,2-dimesitylvinyl Acetates.

The vinyl propellers (E)- and (Z)-2-m-methoxymesityl-1,2-dimesitylvinyl acetates (3c and 3d) were prepared and their geometries assigned. The stereoisomerization barriers of the trimesityl vinyl acetate system were determined by DNMR and by enantioselective LC resolution and polarimetric monitoring of the behavior of the two diastereomeric racemates of 3c and 3d. Combined with data for trimesitylvinyl-OAc 3a and its 1-m-methoxymesityl analogue 3b, the following order of barriers DeltaG() is obtained: alphabeta-2-ring flip > alphabeta'-2-ring flip > betabeta'-2-ring flip > alphabetabeta'-3-ring flip (the threshold enantiomerization barrier). This order which differs from the previously found orders for trimesitylvinyl-X, X = H, OPr-i was rationalized and discussed.

Stable simple enols. Self-catalyzed E/Z-isomerization of the sterically crowded 2-(m-methoxymesityl)-1,2-dimesitylethenol.

(E)-2-(m-methoxymesityl)-1,2-dimesitylethenol (3a) isomerizes in the absence of a catalyst in solution to a 1.0:0.9 E/Z (3a/3b) equilibrium mixture. In CDCl3 the isomerization is first order in 3a within a run, but the plot of the rate constant k(obs) vs the changing [3a]0 in different runs is a half-parabola, indicating self-catalysis by more than one enol molecule. At 0.09 M enol, the isotope effect k(3a)/k(3a)-OD = 2.1. In the presence of 0.025-0.25 M pyridine-d5, the k(obs) vs [pyridine-d5] plot displays a bell-shaped profile. The change in the shape of the OH signals of the 3a/3b mixture at 295-430 K in C6D5NO2 was followed by DNMR. The four signals of the diastereomeric 3a/3b mixture observed at 330 K coalesce at 350 K with barriers of 18.3 and 18.4 kcal x mol(-1) due to the diastereomerization of the vinyl propellers. The resulting two signals observed at >360 K further coalesce at 425 K with a barrier of 22.9 kcal x mol(-1) due either to oxygen-to-oxygen proton exchange or to E/Z isomerization. The estimated upper limit for the rate of proton exchange of k(ex) < or = (2-4) x 10(3) M(-1) x s(-1) at 425 K between the enol molecules is sufficiently slow to be a rate-controlling step in the isomerization. A process in which several enol molecules catalyze the isomerization is suggested, and several mechanistic routes are analyzed.

Stable simple enols. Resolution of chiral 1-[9'-(2'-fluoroanthryl)]-2,2-dimesitylethenol. A different racemization mechanism for the enol and its acetate.

Chiral 1-[9'-(2'-methoxyanthryl)]-2,2-dimesitylethenol (2), 1-[9'-(2'-fluoroanthryl)]-2,2-dimesitylethenol (3), and 1-[9'-(2'-fluoroanthryl)]-2,2- dimesitylvinyl acetate (4) were synthesized and their DNMR behavior in C6D5NO2 was studied. 3 and 4 were resolved on an amylose tris(3,5-dimethylphenylcarbamate) HPLC column to their enantiomers. Acetate 4 racemizes slowly in solution with DeltaG(e)(++), DeltaH(e)(++), and DeltaS(e)(++) values of 26.2, 27.6 kcal mol(-)(1), and 4.3 eu, respectively, as expected for a rotational betabeta'-2-ring flip process in a vinyl propeller and the racemization is unaffected by added TFA, Et3N, and EtOD. Although 3 racemizes almost 350 times faster, the racemization is catalyzed by TFA and shows bell-shape catalysis by Et3N and a KIE in a partially deuteriated solvent. From this and the DNMR data, it is concluded that 3 does not racemize via a rotational betabeta'-2-ring flip. Five nonflip routes are discussed for the racemization of 3, and it is concluded that only the one initiated by protonation at C1 does not contradict the experimental data. By analogy with the E/Z isomerization of the structurally related 2-(m-methoxymesityl)-1,2-dimesitylethenol 17, it is suggested that in the absence of added catalyst one or more enol molecule(s) catalyze the enantiomerization of another one. Only partial resolution was achieved for 2 and from the similarity of its behavior with that of 3, it is suggested that it racemizes by the same mechanism.