28446-70-0Relevant articles and documents
Selective α-Deuteration of Cinnamonitriles using D2O as Deuterium Source
Guo, Beibei,de Vries, Johannes G.,Otten, Edwin
supporting information, p. 179 - 186 (2021/10/12)
The selective α-deuteration of α,β-unsaturated nitriles using the strong base tBuOK or a metal-ligand cooperative Ru pincer catalyst is described. With D2O as deuterium source and glyme as solvent at 70 °C, tBuOK is an efficient catalyst for deuteration at the α-C(sp2) position of cinnamonitriles, providing access to a broad range of deuterated derivatives in good to excellent yields and with very high levels of deuterium incorporation. While the tBuOK-catalysed protocol does not tolerate base-sensitive functional groups, cinnamonitrile derivatives containing a benzylic bromide or ester moiety were deuterated in excellent yields using Milstein's ruthenium PNN pincer catalyst. Moreover, the activity for H/D exchange of the metal-ligand cooperative Ru catalyst is found to be significantly higher than that of tBuOK, allowing reactions to proceed well even at room temperature. A mechanistic proposal is put forward that involves deprotonation of the cinnamonitrile α-CH position when using tBuOK as catalyst, whereas H/D exchange catalysis with the Ru PNN pincer likely proceeds via (reversible) oxa-Michael addition of D2O. (Figure presented.).
Cu-catalyzed cyanomethylation of imines and α,β-alkenes with acetonitrile and its derivatives
Ahmad, Muhammad Siddique,Ahmad, Atique
, p. 5427 - 5431 (2021/02/12)
We describe copper-catalyzed cyanomethylation of imines and α,β-alkenes with a methylnitrile source and provide an efficient route to synthesize arylacrylonitriles and β,γ-unsaturated nitriles. This method tolerates aliphatic and aromatic alkenes substituted with a variety of functional groups such as F, Cl, Br, Me, OMe,tert-Bu, NO2, NH2and CO2H with good to excellent yields (69-98%). These systems consist of inexpensive, simple copper catalyst and acetonitrile with its derivatives (α-bromo/α-iodo-acetonitrile) and are highly applicable in the industrial production of acrylonitriles.
Manganese(I)-Catalyzed H-P Bond Activation via Metal-Ligand Cooperation
Pérez, Juana M.,Postolache, Roxana,Casti?eira Reis, Marta,Sinnema, Esther G.,Vargová, Denisa,De Vries, Folkert,Otten, Edwin,Ge, Luo,Harutyunyan, Syuzanna R.
supporting information, p. 20071 - 20076 (2021/12/03)
Here we report that chiral Mn(I) complexes are capable of H-P bond activation. This activation mode enables a general method for the hydrophosphination of internal and terminal α,β-unsaturated nitriles. Metal-ligand cooperation, a strategy previously not considered for catalytic H-P bond activation, is at the base of the mechanistic action of the Mn(I)-based catalyst. Our computational studies support a stepwise mechanism for the hydrophosphination and provide insight into the origin of the enantioselectivity.
