216590-89-5Relevant articles and documents
Alkynenitriles: chelation-controlled conjugate additions
Fleming, Fraser F.,Gudipati, Venugopal,Steward, Omar W.
, p. 659 - 661 (2002)
Chelation between γ-hydroxybutynenitrile and Grignard reagents triggers a particularly facile anionic conjugate addition reaction. Structurally diverse Grignard reagents add with equal efficiency, providing an intermediate anion that stereoselectively alk
Alkynenitriles: Stereoselective chelation controlled conjugate addition-alkylations
Fleming, Fraser F.,Gudipati, Venugopal,Steward, Omar W.
, p. 5585 - 5593 (2003)
Chelation-controlled conjugate addition of Grignard reagents to γ-hydroxyalkynenitriles stereoselectively generates tri- and tetra-substituted alkenenitriles. t-BuMgCl-initiated deprotonation of hydroxyalkynenitriles followed by addition of a second Grignard reagents triggers a facile conjugate addition leading to a cyclic magnesium chelate. Protonation of the chelate stereoselectively generates trisubstituted nitriles whereas the addition of t-BuLi causes conversion to an 'ate' complex that allows alkylation with aldehyde electrophiles. The chelation-controlled conjugate addition-alkylation generates tri- and tetra-substituted alkenenitriles that are otherwise difficult to synthesize.