A Novel Synthesis of Aromatic <i>N</i>-Chloro Aldimines

Kupfer, René; Brinker, Udo H.

doi:10.1021/jo960171f

Cited by 19 publications

(13 citation statements)

References 12 publications

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“…Synthesis and characterization of orthopalladated complexes 3 a-n: The amino esters and amino phosphonates shown in Figure 1 were prepared by using previously reported methods, [8, [14][15][16][17][18] although in most cases we introduced slight modifications (see the Supporting Information) to optimize the reported procedures. To study the individual effect of each substituent on the CA C H T U N G T R E N N U N G (aryl) À H bond-activation step, we investigated a large set of amino ester based substrates with different substituents in all modifiable points of the molecule; i.e., the N-amine atom, the C-a atom and the aryl ring.…”

Section: Resultsmentioning

confidence: 99%

Cyclopalladation and Reactivity of Amino Esters through CH Bond Activation: Experimental, Kinetic, and Density Functional Theory Mechanistic Studies

Laga

García‐Montero

Sayago

et al. 2013

Chemistry A European J

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The orthopalladation, through CH bond activation, of a large number of amino esters and amino phosphonates derived from phenylglycine, and having different substituents at the aryl ring and the C‐α atom, as well as on the N‐amine atom, has been studied. The experimental observations indicated an improvement in the yields of the orthopalladated compounds when the N‐amine and/or the C‐α atom are substituted, when compared with the unsubstituted methyl phenylglycinate derivatives. In contrast, substitutions at the aryl ring do not promote significant changes in the orthometalation results. Furthermore, the use of hydrochloride salts of the amino esters has also been shown to have a remarkably favorable effect on the process. All these observations have been fully quantified at different temperatures and pressures by a detailed kinetic study in solution in different solvents and in the presence and absence of added Brønsted acids and chloride anions. The data collected indicate relevant changes in the process depending on these conditions, as expected from the general background known for cyclopalladation reactions. An electronic mechanism of the orthopalladation has been proposed based on DFT calculations at the B3LYP level, and a very good agreement between the trends kinetically measured and the theoretically calculated activation barriers has been obtained. The reactivity of the new orthopalladated amino phosphonate derivatives has been tested and it was found that their halogenation, alkoxylation and carbonylation resulted in formation of the corresponding functionalized ortho‐haloaminophosphonates, ortho‐alkoxyaminophosphonates and oxoisoindolinylphosphonates.

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Section: Resultsmentioning

confidence: 99%

Cyclopalladation and Reactivity of Amino Esters through CH Bond Activation: Experimental, Kinetic, and Density Functional Theory Mechanistic Studies

Laga

García‐Montero

Sayago

et al. 2013

Chemistry A European J

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“…General Procedure for the Synthesis of ( E )‐ N ‐Chloro‐1‐phenylmethanimine (4a): Benzylamine ( 1a , 0.212 g, 1.5 mmol) and N ‐chlorosuccinimide ( 2 , 0.400 g, 3 mmol) were milled in a zirconia vial (50 mL) containing two balls ( d = 11.2 mm) of the same material. The reagents were then subjected to ball‐milling in a shaker milling device at room temperature for 10 min(the disappearance of benzylamine was monitored by TLC).…”

Section: Methodsmentioning

confidence: 99%

A Mechanochemical‐Assisted Oxidation of Amines to Carbonyl Compounds and Nitriles

et al. 2017

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A mild, efficient, metal‐ and solvent‐free oxidation of primary amines to aldehydes, ketones, and nitriles under ball‐milling conditions is presented. This method has proved to be compatible with various functional groups and only requires easily accessible starting materials. Simple purification of the reaction mixtures by short‐column chromatography afforded pure aldehydes, ketones, and nitriles as products.

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“…Compounds (VIII) form in yields from moderate to good when the corresponding aldehydes react with saturated aqueous [142][143][144][145][146] or alcoholic [146,147] ammonia solution, more rarely with ammonia solu tion in THF [148], CH 2 Cl 2 , or benzene [147] (Scheme 40). Ammonium chloride is used as a catalyst in some cases [147].…”

Section: Syntheses From Aldehydes and Ammoniamentioning

confidence: 99%