345929-47-7Relevant academic research and scientific papers
The Michael Reaction. Mechanism, Stereochemistry and a Synthetically Useful Modification
Crossland, Ingolf,Hommeltoft, Sven Ivar
, p. 21 - 26 (2007/10/02)
Dimethyl malonate anions react with α,β-unsaturated aldehydes giving products with trans stereochemistry, Scheme 1.The enolate anions may be trapped with trimethylchlorosilane to give the enol ethers 4 with better than 95percent stereoselectivity.Triethylamine, trimethylchlorosilane and acrolein react similarly to give the enol ether 7 with the opposite, i.g. cis, stereochemistry.Dipole minimization in the transition states (Schemes 2 and 3) seems an obvious rationalization of the observed stereochemistry.The triethylamine catalyzed addition of dimethyl nitromalonate to atropaldehyde produces a stereoisomeric mixture of the enols Z-5 and E-5 as the initial products.
