Monoalkylation of primary amines and N-sulfinylamides

Ruano, José Luis Garcı́a; Parra, Alejandro; Alemán, José V.; Yuste, Francisco; Mastranzo, Virginia M.

doi:10.1039/b816846f

Cited by 50 publications

(24 citation statements)

References 32 publications

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“…To our knowledge, limited procedures were reported for the regioselective N -alkylation of N - tert -butanesulfinylamides [27–28]. Following the procedure reported in literature [26], initial experiments were conducted with 4 and 5 , and 4 and 6 in DMF with 2.0 equiv of LiHMDS at −20 °C to room temperature, which resulted in an isolated yield of 40 and 44% pure product, respectively.…”

Section: Resultsmentioning

confidence: 99%

A novel asymmetric synthesis of cinacalcet hydrochloride

Arava

Gorentla²,

Dubey³

2012

Beilstein J. Org. Chem.

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Section: Resultsmentioning

confidence: 99%

A novel asymmetric synthesis of cinacalcet hydrochloride

Arava

Gorentla²,

Dubey³

2012

Beilstein J. Org. Chem.

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“…These expensive catalysts have associated difficulties, such as catalyst–product separation and the necessity for special handling of the metal complexes. Recyclable systems, which have recently been reported, for related reactions use an expensive PGM catalyst (Ru)14a,b or an excess amount of solid promoter (Raney Ni) 14c. Other transition metal‐ and solid acid‐based heterogeneous catalysts have also been used for this reaction, but a high temperature (>200 °C) and/or high H 2 pressure are usually required 7.…”

Section: Introductionmentioning

confidence: 99%

γ‐Alumina‐Supported Silver Cluster for N‐Benzylation of Anilines with Alcohols

2009

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An alumina‐supported silver cluster with a Lewis acidic cocatalyst (polyvalent metal salts, such as FeCl3⋅6 H2O) acts as a heterogeneous and recyclable catalyst for the direct N‐alkylation of anilines with benzyl alcohols, which is driven by the borrowing hydrogen mechanism. Systematic studies on the effects of metal (Pt, Pd, Au, and Ag), silver particle size, support oxides (CeO2, ZrO2, Al2O3, SiO2), and Lewis acidic additives show four important factors required to achieve selective N‐alkylation of anilines: 1) metal with a weak metal–hydrogen bond energy (i.e., Ag), 2) smaller size of the silver cluster, 3) the support having both acidic and basic sites (i.e., Al2O3), and 4) additives with high Lewis acidity (i.e., FeIII salt). Fundamental information will be useful for the rational design of platinum‐group metal‐free heterogeneous catalysts for environmentally benign CN bond forming reactions.

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“…Many of these methods employ transition metal catalysts, including the hydroaminations of alkenes, 13 C-H activation methods, 14 metal catalyzed additions to N-sulfonyl imines, 6b,15 alkylation via π-allyl metal complexes, 16 and alkylation of alcohols via borrowing hydrogen methods. 17 Direct alkylation of benzylic and allylic alcohols and ethers has also been explored, 18 although these methods typically require the use of strong Brønsted or Lewis acids and elevated temperatures.…”

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confidence: 99%

Alkylation of Sulfonamides with Trichloroacetimidates under Thermal Conditions

Wallach

Chisholm

2016

J. Org. Chem.

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An intermolecular alkylation of sulfonamides with trichloroacetimidates is reported. This transformation does not require an exogenous acid, base, or transition metal catalyst, instead the addition occurs in refluxing toluene without additives. The sulfonamide alkylation partner appears to be only limited by sterics, with unsubstituted sulfonamides providing better yields than more encumbered N-alkyl sulfonamides. The trichloroacetimidate alkylating agent must be a stable cation precursor for the substitution reaction to proceed under these conditions. Graphical abstractThe sulfonamide functional group has played an important role in the development of numerous pharmaceuticals. While best known as antibiotics, sulfonamide scaffolds provide a diverse range of biological activity including antitumor, antiviral, diuretic, antiinflammatory and anti-hypertensive properties. 1 Summaries of the top selling pharmaceuticals clearly demonstrate that sulfonamides are well represented in these valuable structures. 2 Data on recently approved pharmaceuticals indicate that sulfonamides continue to be popular in drug discovery, 3 with recent publications in the medicinal chemistry field corroborating that the investigation of sulfonamide-containing structures is ongoing. 4 Sulfonamides also have proven useful in agricultural and insecticidal applications. 5

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Monoalkylation of primary amines and N-sulfinylamides

Abstract: An efficient monoalkylation of primary amines with primary or secondary alcohols catalyzed by Ra-Ni under mild conditions is described.

Cited by 50 publications

References 32 publications

A novel asymmetric synthesis of cinacalcet hydrochloride

A novel asymmetric synthesis of cinacalcet hydrochloride

γ‐Alumina‐Supported Silver Cluster for N‐Benzylation of Anilines with Alcohols

Alkylation of Sulfonamides with Trichloroacetimidates under Thermal Conditions

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