1234618-12-2Relevant academic research and scientific papers
Rhodium-Catalyzed Asymmetric Allylation of Malononitriles as Masked Acyl Cyanide with Allenes: Efficient Access to β,γ-Unsaturated Carbonyls
Grugel, Christian P.,Breit, Bernhard
supporting information, p. 15223 - 15226 (2018/09/25)
A rhodium-catalyzed regio- and enantioselective intermolecular allylation of malononitriles as masked acyl cyanides (MAC) with terminal and symmetrical internal allenes is reported. A RhI/Josiphos catalytic system combined with subsequent oxidative degradation of the primary adducts enables a straightforward access to α-branched, β,γ-unsaturated carbonyl compounds. The present protocol exhibits perfect atom economy in the allylation step and is characterized by a great functional group compatibility. Furthermore, the use of α-substituted malononitriles allowed for the construction of all-carbon quaternary centers.
Iridium-catalyzed kinetic asymmetric transformations of racemic allylic benzoates
Stanley, Levi M.,Bai, Chen,Ueda, Mitsuhiro,Hartwig, John F.
supporting information; experimental part, p. 8918 - 8920 (2010/08/21)
Versatile methods for iridium-catalyzed, kinetic asymmetric substitution of racemic, branched allylic esters are reported. These reactions occur with a variety of aliphatic, aryl, and heteroaryl allylic benzoates to form the corresponding allylic substitution products in high yields (74-96%) with good to excellent enantioselectivity (84-98% ee) with a scope that encompasses a range of anionic carbon and heteroatom nucleophiles. These kinetic asymmetric processes occur with distinct stereochemical courses for racemic aliphatic and aromatic allylic benzoates, and the high reactivity of branched allylic benzoates enables enantioselective allylic substitutions that are slow or poorly selective with linear allylic electrophiles.
