880133-20-0Relevant articles and documents
Magnesiated unsaturated silylated cyanohydrins as synthetic equivalents of aromatic and heterocyclic Grignard reagents bearing a ketone or an aldehyde
Liu, Ching-Yuan,Ren, Hongjun,Knochel, Paul
, p. 617 - 619 (2007/10/03)
The preparation of iodo-substituted aryl, heteroaryl, or cycloalkenyl ketones as silylated cyanohydrins allows the smooth performance of an l/Mg-exchange using i-PrMgCl·LiCl. A facile deprotection of the resulting functionalized products obtained by a rea
Carbopalladation of nitriles: Synthesis of 3,4-disubstituted 2-aminonaphthalenes and 1,3-benzoxazine derivatives by the palladium-catalyzed annulation of alkynes by (2-Iodophenyl)acetonitrile
Tian, Qingping,Pletnev, Alexandre A.,Larock, Richard C.
, p. 339 - 347 (2007/10/03)
Intramolecular carbopalladation of the cyano group has been employed for the synthesis of 3,4-disubstituted 2-aminonaphthalenes. (2-Iodophenyl)acetonitrile reacts with a variety of internal alkynes to afford 2-aminonaphthalenes in high yields with good regioselectivity. The scope and limitations of this process, which proceeds by the intramolecular addition of a vinylpalladium species to the triple bond of the cyano group, have been studied. The annulation of certain hindered propargylic alcohols affords 1,3-benzoxazine derivatives, rather than the expected 2-aminonaphthalenes. The involvement of trialkylamine bases in the formation of these heterocyclic compounds has been established. A proposed mechanism for the synthesis of 1,3-benzoxazine derivatives involves the formation of the expected 2-amino-3-(1-hydroxyalkyl)naphthalenes, followed by their condensation with an iminium ion species formed from the trialkylamine base used in the reaction.
