Zinc‐Catalyzed Chemoselective Reduction of Tertiary and Secondary Amides to Amines

Das, Shoubhik; Addis, Daniele; Junge, Kathrin; Beller, Matthias

doi:10.1002/chem.201101143

Cited by 150 publications

(51 citation statements)

References 86 publications

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“…The production of secondary amines was completely selective in the presence of ester, nitro, nitrile, and ether groups, as well as CÀC double bonds and azo bonds. [32] Besides iron-based catalysts, we also investigated the tetrabutylammonium fluoride (TBAF) catalyzed hydrosilylation of primary amides to amines with methyldiethoxysilane (EtO) 2 MeSiH. [8b, 33] With benzamide as the model substrate, the exclusive formation of benzonitrile took place (Scheme 12).…”

Section: Reduction Of Amidesmentioning

confidence: 99%

Selective Reduction of Carboxylic Acid Derivatives by Catalytic Hydrosilylation

et al. 2011

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In the last decade, an increasing number of useful catalytic reductions of carboxylic acid derivatives with hydrosilanes have been developed. Notably, the combination of an appropriate silane and catalyst enables unprecedented chemoselectivity that is not possible with traditional organometallic hydrides or hydrogenation catalysts. For example, amides and esters can be reduced preferentially in the presence of ketones or even aldehydes. We believe that catalytic hydrosilylations will be used more often in the future in challenging organic syntheses, as the reaction procedures are straightforward, and the reactivity of the silane can be fine-tuned. So far, the synthetic potential of these processes has clearly been underestimated. They even hold promise for industrial applications, as inexpensive and readily available silanes, such as polymethylhydrosiloxane, offer useful possibilities on a larger scale.

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Section: Reduction Of Amidesmentioning

confidence: 99%

Selective Reduction of Carboxylic Acid Derivatives by Catalytic Hydrosilylation

et al. 2011

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“…There are a few examples of the direct hydrogenation of amides; [2] however, silanes are more commonly employed as reducing agents in these methods. [7] Recently, Beller reported the use of copper- [8] and zincbased [9] systems for the catalytic hydrosilylation of secondary and tertiary amides. In 1998, Ito reported the use of an analogue of Wilkinson's rhodium complex for the catalytic hydrosilylation of tertiary amides.…”

Section: Introductionmentioning

confidence: 99%

Direct Hydrosilylation of Tertiary Amides to Amines by an In Situ Formed Iron/N‐Heterocyclic Carbene Catalyst

2013

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Tertiary amides were efficiently reduced to their corresponding tertiary amines in high isolated yields by using the commercially available and inexpensive polymeric silane polymethylhydrosiloxane (PMHS) as the reducing agent. The reaction is efficiently catalyzed by an in situ generated iron/N‐heterocyclic carbene complex (1 mol‐%) obtained from iron(II) acetate and 1‐(2‐hydroxy‐2‐phenylethyl)‐3‐methylimidazolium triflate ([PhHEMIM][OTF]). A catalytic amount of lithium chloride (1 mol‐%) present in the reaction mixture significantly reduced the reaction time and increased the chemoselectivity of the reduction process.

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“…Notably, the reduction of different classes of primary, secondary, and tertiary amides requires different catalysts and reaction conditions according to their different reactivity pattern. So far most of the catalysts work for tertiary amides,11, 12, 14–19 compared to secondary13a, 14e, 17 and primary amides 13b. 14e, 17 It should be noted, that no other catalytic reduction methodology offers such a diversity of potential catalysts 20.…”

Section: Methodsmentioning

confidence: 99%

Selective Rhodium‐Catalyzed Reduction of Tertiary Amides in Amino Acid Esters and Peptides

Das

Bornschein

et al. 2015

Angewandte Chemie

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Efficient reduction of the tertiary amide bond in amino acid derivatives and peptides is described. Functional group selectivity has been achieved by applying acommercially available rhodium precursor and bis(diphenylphosphino)propane (dppp) ligand together with phenyl silane as areductant. This methodology allows for specific reductive derivatization of biologically interesting peptides and offers straightforward access to av ariety of novel peptide derivatives for chemical biology studies and potential pharmaceutical applications.The catalytic system tolerates av ariety of functional groups including secondary amides,e ster,n itrile,t hiomethyl, and hydroxy groups.T his convenient hydrosilylation reaction proceeds at ambient conditions and is operationally safe because no air-sensitive reagents or highly reactive metal hydrides are needed.

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Zinc‐Catalyzed Chemoselective Reduction of Tertiary and Secondary Amides to Amines

Cited by 150 publications

References 86 publications

Selective Reduction of Carboxylic Acid Derivatives by Catalytic Hydrosilylation

Selective Reduction of Carboxylic Acid Derivatives by Catalytic Hydrosilylation

Direct Hydrosilylation of Tertiary Amides to Amines by an In Situ Formed Iron/N‐Heterocyclic Carbene Catalyst

Selective Rhodium‐Catalyzed Reduction of Tertiary Amides in Amino Acid Esters and Peptides

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