352015-01-1Relevant articles and documents
Highly efficient chiral copper Schiff-base catalyst for asymmetric cyclopropanation of 2,5-dimethyl-2,4-hexadiene
Itagaki, Makoto,Hagiya, Koji,Kamitamari, Masashi,Masumoto, Katsuhisa,Suenobu, Katsuhiro,Yamamoto, Yohsuke
, p. 7835 - 7843 (2004)
A remarkable increase in catalytic activity is found for the asymmetric cyclopropanation of 2,5-dimethyl-2,4-hexadiene with diazoacetate by use of the chiral copper Schiff-base complexes, which are derived from substituted salicylaldehydes, chiral aminoalcohols, and copper acetate monohydrate. Furthermore, a combination of a chiral copper Schiff-base with a Lewis acid showed an increase in yield (up to 90%) and in enantioselectivity (up to 90% ee) for the asymmetric cyclopropanation of the diene with t-butyl diazoacetate at 20°C.
Practical copper-catalyzed asymmetric synthesis of chiral chrysanthemic acid esters
Itagaki, Makoto,Suenobu, Katsuhiro
, p. 509 - 518 (2012/12/31)
Practical copper salicylaldimine complex catalysts have been developed for the asymmetric synthesis of chiral chrysanthemic acid esters by the cyclopropanation reaction of 2,5-dimethyl-2,4-hexadiene with tert-butyl diazoacetate. First, the effects of the substituents on the salicylaldehyde moiety in the copper salicylaldimine complex (copper Schiff base complex) on the catalytic activity and the stereoselectivities were investigated. As a result, a substitution of hydrogen at the 5-position with the nitro group on the salicylaldehyde moiety was found to enhance the catalytic efficiency. In addtition, a combination catalyst of the copper Schiff base complex with Lewis acid was found to also enhance the catalytic efficiency and achieved 90% chemical yield and 91% ee at 20 °C with 0.1 mol % catalyst loading. Furthermore, the asymmetric induction mechanism of the cyclopropanation reaction catalyzed by the copper Schiff base complex was studied using density functional calculations.
