posted on 2016-02-18, 20:48authored byXianglin Shi, William F. Kiesman, Anna Levina, Zhili Xin
Binaphthol-catalyzed
asymmetric Petasis reactions of salicylaldehydes
with dibutyl vinylboronates and secondary amines in the presence of
4 Å molecular sieves (MS) afforded products with up to 99% ee
in isolated yields of 39–94%. The 99% ee of the product indicated
that the reaction by the binaphthol-catalyzed pathway was roughly
500 times faster than the uncatalyzed pathway. NMR experiments (1H and 11B) showed that the amine component played
a role in triggering the reaction between the binaphthol catalyst
and the vinylboronate in the catalytic reaction sequence. The 4 Å
MS enhanced both the rate and enantioselectivity by effective removal
of water from the reaction system. A novel rearrangement reaction
of the unconjugated allylic amine Petasis reaction product to a conjugated
allylic amine was also observed.