1078710-10-7Relevant academic research and scientific papers
Stereoselective alkylations of chiral nitro imine and nitro hydrazone dianions. Synthesis of enantiomerically enriched 3-substituted 1-nitrocyclohexenes
Denmark, Scott E.,Ares, Jeffrey J.
supporting information; experimental part, p. 9647 - 9656 (2009/04/11)
(Chemical Equation Presented) Dianions of chiral nitro imines (generated by a combination of LDA and s-BuLi) underwent diastereoselective alkylation with methyl, butyl, isopropyl, allyl, and methallyl iodides. In contrast to the behavior of simple metalloenamines, the most selective auxiliary contained no coordinating groups but did possess a large steric difference between the two substituents. The yield and selectivity of the alkylations were improved by the addition of HMPA or DMPU. The use of (S)-1-naphthylethylamine as the auxiliary afforded the R absolute configuration of the alkylation products. This stereochemical outcome could be rationalized by simple steric approach controlled alkylation in a conformationally fixed, internally coordinated dianion. A SAMP nitro hydrazone gave poorer yields and selectivities.
