Reduction of amides with NaBH4 in diglyme at 162 °C

Zhu, Hua‐Jie; Lu, Kaitao; Sun, Guang-Ri; He, Jinbao; Li, Haiqing; Pittman, Charles U.

doi:10.1039/b208464c

Cited by 13 publications

(12 citation statements)

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“…[12] Reports of the use of the less aggressive reducing agent NaBH 4 towards reduction of amides at high temperatures [13,14] are also instructive. Here, secondary amides are unreactive, tertiary amides give the corresponding amine in moderate yield, whereas primary amides undergo initial dehydration to the nitrile followed by slow reduction to the amine, a point that may be of significance in mechanistic terms.…”

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confidence: 98%

Selective Hydrogenation of Amides using Ruthenium/ Molybdenum Catalysts

et al. 2010

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Recyclable, heterogeneous bimetallic ruthenium/molybdenum catalysts, formed in situ from triruthenium dodecacarbonyl [Ru 3 (CO) 12 ] and molybdenum hexacarbonyl [Mo(CO) 6 ], are effective for the selective liquid phase hydrogenation of cyclohexylcarboxamide (CyCONH 2 ) to cyclohexanemethylamine (CyCH 2 NH 2 ), with no secondary or tertiary amine by-product formation. Variation of Mo:Ru composition reveals both synergistic and poisoning effects, with the optimum combination of conversion and selectivity at ca. 0.5, and total inhibition of catalysis evident at ! 1. Good amide conversions are noted within the reaction condition regimes 20-100 bar hydrogen and 145-160 8C. The order of reactivity of these catalysts towards reduction of different amide functional groups is primary > tertiary @ secondary. In situ HP-FT-IR spectroscopy confirms that catalyst genesis occurs during an induction period associated with decomposition of the organometallic precursors. Ex situ characterisation, using XRD, XPS and EDX-STEM, for active Mo:Ru compositions, has provided evidence for intimately mixed ca. 2.5-4 nm particles that contain metallic ruthenium, and molybdenum (in several oxidation states, including zero).

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confidence: 98%

Selective Hydrogenation of Amides using Ruthenium/ Molybdenum Catalysts

et al. 2010

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“…The gene (NfdA) encoding this enzyme was also cloned (Fukatsu et al, 2004). NBFA is of great importance for the reduction with NaBH 4 to benzylmethylamine (Zhu et al, 2003). The conformational analysis of NBFA was performed with the help of density functional theory and second-order Møller-Plesset (MP2) calculations (Vargas et al, 2001;Robertson et al, 2000).…”

Section: Commentmentioning

confidence: 99%

N-Benzylformamide at 150 K

2008

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The title compound, C(8)H(9)NO, crystallizes with Z' = 2. Each type of independent molecule links into a separate N-H...O hydrogen-bonded chain in the a-axis direction. There are also three weak C-H...O hydrogen bonds, which join the molecules into a two-dimensional sheet parallel to (001). The molecules exhibit the trans conformation of the -NHCHO group and an anti conformation around the (Ph)C-NH(CHO) bond. The formamide group in each of the symmetry-independent molecules is twisted out of the benzyl group plane, forming angles of 75.96 (10) and 65.23 (11) degrees with this plane. The significance of this study lies in the comparison drawn between the experimental and calculated data of the crystal structure of the title compound and the data of several other derivatives possessing the -CH(2)-NH-CO- group. The correlation between the IR spectrum of this compound and the hydrogen-bond energy is also discussed. This molecular system is of particular interest to biochemists because of its preventative function against toxic products of alcohols in human metabolism.

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“…44 However, the addition of LiCl to the NaBH 4 -diglyme system increases the rate of primary aromatic amide and aromatic nitrile conversion to both the nitrile first, and the amine. The mechanism proposed by Pittman Jr and co-workers for the reduction of primary aromatic amides was based on the initial evolution of one mole equivalent of hydrogen and formation of the nitrile, followed by reduction to the amine (Scheme 15).…”

Section: Reduction Of Amides Nitriles Azides and Iminesmentioning

confidence: 99%

Recent methodologies mediated by sodium borohydride in the reduction of different classes of compounds

Souza

Vasconcelos

2006

Applied Organom Chemis

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Reduction is a fundamental transformation in organic synthesis. Since its discovery by Brown and co-workers, sodium borohydride is the most frequently hydride used in reduction processes. Owing to the importance of this reagent in modern organic synthesis, the aim of this review is to highlight recent methodologies (2000-2006) mediated by sodium borohydride in the reduction of different classes of compounds. REDUCTION OF ALDEHYDES AND KETONESChadha and Kumar have developed a simple and efficient one-pot reaction for reduction and transesterification of β-keto esters, 1, under mild conditions to produce the

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Reduction of amides with NaBH4 in diglyme at 162 °C

Cited by 13 publications

References 11 publications

Selective Hydrogenation of Amides using Ruthenium/ Molybdenum Catalysts

Selective Hydrogenation of Amides using Ruthenium/ Molybdenum Catalysts

N-Benzylformamide at 150 K

Recent methodologies mediated by sodium borohydride in the reduction of different classes of compounds

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