Liu Y, Hu H, Zheng H, Xia Y, Liu X, Lin L, Feng X * Sichuan University, Chengdu and
Lanzhou University, P. R. of China
Nickel(II)-Catalyzed Asymmetric Propargyl and Allyl Claisen Rearrangements to Allenyl-
and Allyl-Substituted β-Ketoesters.
Angew. Chem. Int. Ed. 2014;
53: 11579-11582
Key words
Claisen rearrangement - allenyls - nickel
Significance
The authors present an asymmetric propargyl and allyl Claisen rearrangement using
a readily available chiral N,N′-dioxide–nickel(II) complex. Product allyl and allenyl compounds were obtained with
good yield and excellent enantio- and diastereoselectivities.
Comment
This rearrangement works with relatively inexpensive metal (nickel) under mild reaction
conditions. The produced β-keto esters with all-carbon quaternary stereogenic centers
with allenyl and allyl substituents are highly useful chiral building blocks.
