Schmidt Reaction with Aldehydes and Carboxylic Acids

Koldobskii, G. I.; Островский, В. А.; Gidaspov, B. V.

doi:10.1070/rc1978v047n11abeh002294

Cited by 31 publications

(12 citation statements)

References 29 publications

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“…2.2. 16α-Azido-3-methoxyestra-1,3,5 (10)-trien-17α-ol (2) and 16αazido-3-methoxyestra-1,3,5 (10)-trien-17β-ol (3) Compound 1 (16α-azido-3-methoxyestra-1,3,5(10)-trien-17-one) [11] (3.25 g, 10 mmol) was dissolved in MeOH (250 ml) containing a few drops of EtOAc. To the stirred solution was added 2.46 g, (10 mmol) anhydrous CeCl 3 .…”

Section: Generalmentioning

confidence: 99%

“…Mechanistically, it can be presumed [10] that the first step in the Schmidt reaction involves hemiacetal formation between the aromatic aldehyde and steroid azidoalcohol 2, which undergoes elimination to afford the benzyl carbocation 4. Intramolecular attack of the azide group on the carbocation furnishes intermediate 5, and subsequent proton elimination and N 2 detachment give product 6.…”

Section: Synthetic Studiesmentioning

confidence: 99%

“…In our approach to the synthesis of these new type of steroid heterocycles, we used the Schmidt rearrangement using alkyl azides and benzaldehydes in the presence of Lewis acids [10]. In the case of vicinal azidoalcohols, the intermediate of the rearrangement reacts with the sterically favourable neighbouring hydroxy function resulting in a ringclosure reaction to produce an oxazoline moiety condensed to the sterane D-ring in the 16α,17α positions.…”

Section: Introductionmentioning

confidence: 99%

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Novel preparation of substituted oxazolines condensed to d-ring of estrane skeleton and characterization of their antiproliferative properties

et al. 2021

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Section: Generalmentioning

confidence: 99%

Section: Synthetic Studiesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Novel preparation of substituted oxazolines condensed to d-ring of estrane skeleton and characterization of their antiproliferative properties

et al. 2021

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“…It was also found that primary amides could transfer to the related nitriles by ZnCl 2 in CH 3 CN/H 2 O medium under microwave irradiation. [27] After we have studied the dehydration of amides to nitriles with hydrido iron or cobalt complexes as catalysts, [7][8][9][10][11][12][13][14][15][16][17][18]28] now we want to know if Lewis acids can promote these catalytic systems. Therefore, in order to expand the scope of the application of these hydrido iron complexes, four [PSiP]-pincer iron hydrides 1-4 were synthesized ( Figure 1) and their catalytic activities for dehydration of amides to nitriles were explored.…”

Section: Introductionmentioning

confidence: 99%

“…In traditional synthetic methods, stoichiometric acidic dehydrating or basic reagents . azides, or amine oxidation reagents were used. However, the drawbacks of these processes are obvious, such as harsh reaction conditions, toxic reagents and unfavorable formation of side products.…”

Section: Introductionmentioning

confidence: 99%

Lewis acid promoted dehydration of amides to nitriles catalyzed by [PSiP]‐pincer iron hydrides

Chang

Zhang

et al. 2020

Applied Organom Chemis

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The dehydration of primary amides to their corresponding nitriles using four [PSiP]‐pincer hydrido iron complexes 1–4 [(2‐Ph2PC6H4)2MeSiFe(H)(PMe3)2 (1), (2‐Ph2PC6H4)2HSiFe(H)(PMe3)2 (2), (2‐(iPr)2PC6H4)2HSiFe(H)(PMe3)2 (3) and (2‐(iPr)2PC6H4)2MeSiFe(H)(PMe3)2 (4)] as catalysts in the presence of (EtO)3SiH as dehydrating reagent was explored in the good to excellent yields. It was proved for the first time that Lewis acid could significantly promote this catalytic system under milder reaction conditions than other Lewis acid‐promoted system, such as shorter reaction time or lower reaction temperature. This is also the first example that dehydration of primary amides to nitriles was catalyzed by silyl hydrido iron complexes bearing [PSiP]‐pincer ligands with Lewis acid as additive. This catalytic system has good tolerance for many substituents. Among the four iron hydrides 1 is the best catalyst. The effects of substituents of the [PSiP]‐pincer ligands on the catalytic activity of the iron hydrides were discussed. A catalytic reaction mechanism was proposed. Complex 4 is a new iron complex and was fully characterized. The molecular structure of 4 was determined by single crystal X‐ray diffraction.

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The Schmidt Reaction

et al. 2012

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The classical form of the Schmidt reaction involves the reaction of a carbon‐centered electrophile with hydrazoic acid with loss of nitrogen, usually with a rearrangement that forms a new carbon‐nitrogen bond. Although the conversion of a ketone into an amide is the most commonly used variation, mechanistically related versions utilize an aldehyde, acid, or a carbocation generated from an alkene or alcohol as the electrophilic component. In recent years, the definition of the Schmidt reaction has been modified to include analogous reactions in which the hydrazoic acid is replaced by an alkyl azide, promoted by Lewis acids. The use of an alkyl azide uniquely permits the formulation of intramolecular Schmidt reactions of the azide with a carbonyl or carbocationic electrophile.

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Schmidt Reaction with Aldehydes and Carboxylic Acids

Cited by 31 publications

References 29 publications

Novel preparation of substituted oxazolines condensed to d-ring of estrane skeleton and characterization of their antiproliferative properties

Novel preparation of substituted oxazolines condensed to d-ring of estrane skeleton and characterization of their antiproliferative properties

Lewis acid promoted dehydration of amides to nitriles catalyzed by [PSiP]‐pincer iron hydrides

The Schmidt Reaction

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