Efficient and selective hydration of nitriles to amides in aqueous systems with Ru(II)-phosphaurotropine catalysts

Copper(II) and Sodium(I) Complexes based on 3,7‐Diacetyl‐1,3,7‐triaza‐5‐phosphabicyclo[3.3.1]nonane‐5‐oxide: Synthesis, Characterization, and Catalytic Activity

“…The role of water in such an oxidation process was reported by Frost et al [24] for related systemsi nw hich DAPTAw as oxidized to DAPTA = O + 2H + .I no ur case, this oxidation process is presumably combined with the reduction of Cu II (Scheme 3, route 1) or Ni II (Scheme 3, route 2). To prove the role of water in the DAPTAo xidation process, the synthesis of 1 was undertaken under an inert N 2 atmosphere by using freshly dried solvents and 18 O-labeled water (H 2 18 O) in the reactionm edium (see the Experimental Section). The obtained material was analyzed by using ESI(+ +)-MS, and the spectrum revealed as et of fragments attributable to DAPTA = O 18 (see the Experimental Sectionand Figure S1 in the Supporting Information).…”

“…Among the large family of open‐cage PTA derivatives, 3,7‐diacetyl‐1,3,7‐triaza‐5‐phosphabicyclo[3.3.1]nonane (DAPTA) is a relevant one (Figure ), and its binding capacity has been intensively studied for the Cu, Ru, Rh, Pd, Pt, and Au transition metals to produce complexes that are used mainly for biological applications and, to a lesser extent, for catalysis . The DAPTA ligand usually exhibits the P‐coordination mode to the metal center, and recently, the N‐coordination mode was also reported .…”

“…[7][8][9][10] Among the large family of open-cage PTAd erivatives, [2,11] 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane (DAPTA) is ar elevant one (Figure 1), [11a, 12] and its binding capacity has been intensively studied for the Cu, Ru, Rh, Pd, Pt, and Au transition metals to produce complexes that are used mainly for biological applications [13][14][15][16] and, to al esser extent, for catalysis. [17][18][19][20] The DAPTAl igand usually exhibits the P-coordination modet ot he metal center, [12][13][14][15][20][21][22][23] and recently,t he N-coordination mode wasa lso reported. [17] Although DAPTAh as two coordination sites from the acetyl oxygen atoms, the O-coordination modeo fD APTAhas not yet been reported.…”

Ultrasonic-assisted ruthenium-catalyzed oxidation of some organic compounds in aqueous medium

“…Recently, Kathó et al [12] reported the catalytic hydration of benzonitrile to benzamide in 99% yield by the ruthenium(II) complex, [RuCl 2 (DMSO) 4 ], with the various water-soluble phosphines at reflux temperature. This really encourages us to investigate our catalyst system for hydration of some nitriles to their respective amides.…”

Water soluble diphosphine ligands based on 1,3,5-triaza-7-phosphaadamantane (PTA-PR2): Synthesis, coordination chemistry, and ruthenium catalyzed nitrile hydration

“…[1][2][3] Ruthenium compounds have been utilized as catalysts for nitrile hydration with [(η 6 -arene)RuCl 2 PR 3 ] complexes as some of the most efficient and versatile catalysts with good substrate tolerance. [1][2][3][4][5][6][7][8][9][10][11][12][13][14] Ruthenium complexes of 1,3,5-triaza-7-phosphaadamtane (PTA) [11,12,[15][16][17] and derivatives [10] have exhibited high activity and selectivity for the hydration of nitriles to amides. We have shown that some ruthenium complexes with PTA or PTA derivatives are active for nitrile hydration in the presence of air, removing the need to run these reactions under inert atmosphere.…”