Ruthenium‐catalyzed Selective Monoamination of Vicinal Diols

Abstract

The monoamination of vicinal diols in the presence of in situ generated ruthenium catalysts has been investigated. Among the various phosphines tested in combination with [Ru(3)(CO)(12)], N-phenyl-2-(dicyclohexyl-phosphanyl)pyrrole showed the best performance. After optimization of the reaction conditions this system was applied to different secondary amines and anilines as well as a number of vicinal diols. With the exception of ethylene glycol, monoamination of the vicinal diols occurred selectively and the corresponding amino alcohols were obtained in good yields, producing water as the only side product.

Selective Ruthenium‐Catalyzed Alkylation of Indoles by Using Amines

“…Elegant applications of this general methodology came from the groups of Williams, [6] Yus, [7] Fujita, [8] Grigg, [9] and us. [10] Based on our continuing interest in the activation of amines [11] and the synthesis of novel indoles, [12] we had the idea to apply the former methodology for the derivatization of this important class of natural products. As a result, the reaction of indoles with amines was studied.…”

Ruthenium-Catalyzed Amination of Secondary Alcohols Using Borrowing Hydrogen Methodology

“…Beller and co-workers had previously reported the regioselective amination of 1-phenyl-1,2-ethanediol [(2 mol % Ru 3 CO 12 and N -phenyl-2-(dicyclohexyl-phosphanyl)pyrrole (CataCXium PCy)], although the maximum yield reported with aniline was 55%. 7 Similarly, Oe reported the regioselective amination of 1-phenyl-1,2-ethanediol with secondary amines (5 mol% Ru and ( S,R )-Josiphos). 8 …”

Selective Catalytic Reductions of Amides and Nitriles to Amines

“…Examples include the aminations of olefins and alkynes [16][17][18][19][20][21][22][23], catalytic hydroaminomethylations [24][25][26][27][28][29][30], and more recently amination of alcohols as well as amines [31][32][33][34][35][36][37][38]. Our work on the development of novel catalytic reductions to give amines started around 2007 when we got interested in the ruthenium-catalyzed hydrogenation of nitriles.…”