2014
DOI: 10.1021/ja506023f
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Highly Versatile Catalytic Hydrogenation of Carboxylic and Carbonic Acid Derivatives using a Ru-Triphos Complex: Molecular Control over Selectivity and Substrate Scope

Abstract: The complex [Ru(Triphos)(TMM)] (Triphos = 1,1,1-tris(diphenylphosphinomethyl)ethane, TMM = trimethylene methane) provides an efficient catalytic system for the hydrogenation of a broad range of challenging functionalities encompassing carboxylic esters, amides, carboxylic acids, carbonates, and urea derivatives. The key control factor for this unique substrate scope results from selective activation to generate either the neutral species [Ru(Triphos)(Solvent)H2] or the cationic intermediate [Ru(Triphos)(Solven… Show more

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Cited by 245 publications
(168 citation statements)
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“…Cole-Hamilton 12, 13 , Leitner/Klankermayer 1315 , and Beller 16 have developed different (triphos)Ru catalyst systems (triphos = CH 3 C[CH 2 PPh 2 ] 3 ; Ph = C 6 H 5 ) for selective cleavage of the C=O bond of amides. When combined with catalytic Yb(OSO 2 CF 3 ) 3 , hydrogen pressure ( P H2 ) can be reduced as low as ca.…”
Section: Introductionmentioning
confidence: 99%
See 1 more Smart Citation
“…Cole-Hamilton 12, 13 , Leitner/Klankermayer 1315 , and Beller 16 have developed different (triphos)Ru catalyst systems (triphos = CH 3 C[CH 2 PPh 2 ] 3 ; Ph = C 6 H 5 ) for selective cleavage of the C=O bond of amides. When combined with catalytic Yb(OSO 2 CF 3 ) 3 , hydrogen pressure ( P H2 ) can be reduced as low as ca.…”
Section: Introductionmentioning
confidence: 99%
“…Use of a combination of ( P , C , P )Ir pincer complex and stoichiometric B(C 6 H 5 ) 3 was also proved to be effective for inducing the C=O bond cleavage 17 . In contrast, Ru complexes for the selective cleavage of the C–N bond of amides were intensively studied by Ikariya (( P , N H)Ru) 1821 , Milstein ([ P ,( N , N ) bpy ]Ru, where bpy = bipyridine; ( N , N ) bpy  = bipyridine nitrogens) 2225 , Bergens ([( P , N H 2 )( P , N H 2 )]Ru) 2628 , Leitner/Klankermayer, ((triphos)Ru) 15 , and Beller (( P , N H, N )Ru) 29 . Milstein’s milestone discovery, in which deprotonation at the 2-(pyridyl)methylene unit in the ( P , N py , P)Ru pincer complexes induces an active catalyst 30 , has had a great impact on the ensuing molecular design of hydrogenation catalysts (py = pyridine; N py  = pyridine nitrogen).…”
Section: Introductionmentioning
confidence: 99%
“…While aliphatic CAs generally represent excellent substrates for the present hydrogenation strategy, the hydrogenation of benzoic acid (CA- w ) has rarely been examined 1821, 43 . Indeed, hydrogenation of CA- w with Re- a proceeded sluggishly even under slightly harsher conditions ( P H2  = 4 MPa, 180 °C, 24 h), affording benzyl alcohol (AL- w ) in 29% yield (Fig.…”
Section: Resultsmentioning
confidence: 99%
“…For comparison, AL- w is generated in 93% (95% selectivity) and 62% yield under harsher conditions using a Ru-triphos (2 mol%, P H2  = ca. 5 MPa, 220 °C, 24 h) 21 and Co-triphos complex (2.5 mol%, P H2  = ca. 8 MPa, 100 °C, 22 h) 19 , respectively.
Figure 3Improved chemoselective hydrogenation of CAs and hydrogenolysis of the resulting α-alkoxy alcohols using Re-b.
…”
Section: Resultsmentioning
confidence: 99%
“…[52] The TMM ligand appears to be very labile and readily decomplexes under reducing conditions generating the active catalyst. Near quantitative yields of 1,4-PDO were obtained from levulinic acid and methyl levulinate at 50 bar H 2 and 140 o C (table 2, entry 10).…”
Section: Hydrogenation Of Levulinic Acid (La) To 14-pentanediol (14mentioning
confidence: 99%