116072-08-3Relevant academic research and scientific papers
SYNTHEIEC STUDIES TOWARDS GELSEMINE , I. THE IMPORTANCE OF THE ANTIPERIPLANAR EFFECT IN THE HIGHLY REGIOSELECTIVE REDUCTION OF NON-SYMMETRICAL CIS-HEXAHYDROPHTHALIMIDES.
Vijn, Robert J.,Hiemstra, Henk,Kok, Joost J.,Knotter, Martin,Speckamp, W. Nico
, p. 5019 - 5030 (1987)
During studies aimed at the total synthesis of gelsemine an exceptional example of regioselectivity has been discovered. cis-Hexahydrophthalimides, which are non-symmetrical through the presence of the one alkyl group (see Figure 1), are reduced by sodium borohydride into the corresponding hydroxy lactams with very high regioselectivity.The corresponding cis-tetrahydrophthalimides exhibit much lower selectivity.These findings are explained on the basis of the conformational preference of the imide molecule and the antiperiplanar effect.
Synthetic Studies toward Gelsemine. 2. Preparation of the Tetracyclic Skeletal Part by Way of a Highly Stereospecific Intramolecular Reaction of a Silyl Enol Ether with an N-Acyliminium Ion
Hiemstra, Henk,Vijn, Robert Jan,Speckamp, W. Nico
, p. 3882 - 3884 (2007/10/02)
The tetracyclic skeletal part of the oxindole alkaloid gelsemine (1) was prepared from (E)-3,5-hexadien-1-ol in nine steps, including as the key step an unprecedented stereospecific cyclization reaction of a triisopropylsilyl enol ether with an N-acyliminium ion intermediate to give a tricyclic aldehyde (3 -> 4).
