Reaction of phenylmagnesium bromide with acetonitrile

Abstract

methoxy phthalide isoquinoline (-)-cordrastine II2 (3c). In contrast, boron tribromide under similar reaction conditions was not selective and cleaved 3a to give mainly the corresponding tetraphenol.2 This may be related to the stronger nucleophilic character of the bromide ion.The above transformations demonstrate that boron trichloride can be used to selectively cleave a methylenedioxy group in methoxy-substituted aromatic compounds.Experimental Section® 4,5-Dimethylcatechol (lb).-To 378 mg (2.5 mmol) of 4,5methylenedioxy-o-xylene4 (la) dissolved in 70 ml of methylene chloride was added at room temperature 5 ml of a methylene chloride solution containing 585 mg (5 mmol) of boron trichloride. The solution was stored at ambient temperature for 3 hr; 5 ml of methanol was added and evaporated. The residue was crystallized from a mixture of benzene and petroleum ether to give 300 mg (80%) of lb, mp 89-91°, identical in mixture melting point and tic with authentic 4,5-dimethylcatechol.6 Under these reaction conditions 4,5-dimethoxy-o-xylene6 (lc) was recovered

Facile Synthesis of the CERT Inhibitor HPA‐12 and Some Novel Derivatives

“…Towards this end, we planned to reduce the protected serine to the corresponding serinol and to substitute the newly formed hydroxy group by a nitrile. Nitriles have been reported to be readily attacked by C‐nucleophiles like Grignard reagents to yield the respective ketones 13. The latter then can be stereoselectively reduced, as shown before in the HPA synthesis by Ueno et al.,14 followed by deprotection and N ‐acylation to give the desired HPA‐12 (Scheme ).…”

“…After formation of Garners aldehyde 2, [11] the second chiral center is formed upon nucleophilic attack of the aldehyde by either an alkyne lithium that is subsequently reduced to an E-olefin [11] or, alternatively, by treatment with vinylmagnesium bromide and subsequent olefin metathesis. [13] The latter then can be stereoselectively reduced, as shown before in the HPA synthesis by Ueno et al, [14] followed by deprotection and N-acylation to give the desired HPA-12 (Scheme 1 B). We thus decided to just shift the position for a nucleophilic attack by one methylene group.…”

“…Nitriles have been reported to be readily attacked by C-nucleophiles like Grignard reagents to yield the respective ketones. [13] The latter then can be stereoselectively reduced, as shown before in the HPA synthesis by Ueno et al, [14] followed by deprotection and N-acylation to give the desired HPA-12 (Scheme 1 B).…”

Unexpected Thorpe Reaction of an α-Alkoxynitrile

“…It is noteworthy that even acetonitrile tends to react abnormally with Grignard reagents, e.g. with phenylmagnesium bromide, only 42% of the expected acetophenone has been obtained along with 32% of benzene [15]. Nitriles lacking α-hydrogens react normally and afford ketones.…”

Synthesis of a Five-Fold-Differentiated 1,3,5,7,9-Pentasubstituted Corannulene: A Maximal Labeling Problem in the Context of Corannulene

“…The Grignard reagent of α-chloro-m-xylene reacted with propionitrile and after hydrolysis gave 1-(3-methylphenyl)-2-butanone 1 (Scheme 4). 13 Aldol reaction between 1 and the enolate of pinacolone, generated at -78 °C with LDA, produced carbinol 2. Acidic treatment with HBr induced a cyclization rearomatization to form 1-tert-butyl-3-ethyl-6-methylnaphthylene (3) as a clean product.…”