Abstract:Substituted vinylbenzotriazoles were efficiently converted to benzotriazolyl epoxides by dimethyldioxirane. The behavior of these epoxides toward nucleophiles and strong bases was investigated.
“…3-Hydroxy-1,2-diones have earlier been prepared by either the oxidation of 2-hydroxy-2-ene-1-ones,25a the hydrolysis of the corresponding imines 25b or ring opening of diepoxy ketones,25c the oxidation and subsequent hydrolysis of α-acetoxyacetylenes,25d or the oxidation of 3(2 H )-furanone 25e (Scheme ). α-Alkyl and α-( α-hydroxyalkyl)-benzotriazolyloxiranes of the type 5a , b , e , f have already been utilized for the synthesis of corresponding α-hydroxy ketones 18a. Similarly, treatment of α-acylbenzotriazolyloxiranes 5g , h with perchloric acid readily gave 3-hydroxy-1,2-diones 7a and 7b in 73 and 86% yield, respectively (Scheme ).…”
Section: Resultsmentioning
confidence: 99%
“…3-Hydroxy-1,3,3-triphenyl-1,2-propanedione ( 7a ) and 1-(1-hydroxycyclohexyl)-2-phenyl-1,2-ethanedione ( 7b ) were prepared according to the general procedure reported previously 18a…”
Section: Methodsmentioning
confidence: 99%
“…Benzotriazolyloxiranes have earlier been prepared by the epoxidation of 1-(1-alkenyl)benzotriazoles using m -CPBA18a and dimethyldioxirane 18b. The hydrolysis of α-alkyl- and α-(α-hydroxyalkyl)-benzotriazolyloxiranes gives the corresponding α-hydroxy ketones 18a.…”
Section: Introductionmentioning
confidence: 99%
“…Benzotriazolyloxiranes have earlier been prepared by the epoxidation of 1-(1-alkenyl)benzotriazoles using m -CPBA18a and dimethyldioxirane 18b. The hydrolysis of α-alkyl- and α-(α-hydroxyalkyl)-benzotriazolyloxiranes gives the corresponding α-hydroxy ketones 18a. We now report another convenient and general method for the preparation of benzotriazolyloxiranes and their further transformations to octa-1,7-dien-4-ols and 3-hydroxy-1,2-diones.…”
1-Benzotriazolylchloromethyllithium generated from 1-chloromethylbenzotriazole (1) and LDA reacts with enolizable and nonenolizable ketones to give benzotriazolyloxiranes 2a-g in good yields. The oxiranyllithiums 4a-d generated from 2a-d and n-BuLi at -78 degrees C were trapped by a variety of electrophiles to give oxiranyl derivatives 5a-j in good to excellent yields. Lewis-acid-promoted nucleophilic ring opening of benzotriazolyloxiranes 2a,f,g with allyltrimethylsilane gave the corresponding 1,7-octadien-4-ols 6a-c in 68-75% yield. Hydrolysis of alpha-acylbenzotriazolyloxiranes 5g,h provided 3-hydroxy-1,2-diones 7a and 7b in 73 and 86% yield, respectively.
“…3-Hydroxy-1,2-diones have earlier been prepared by either the oxidation of 2-hydroxy-2-ene-1-ones,25a the hydrolysis of the corresponding imines 25b or ring opening of diepoxy ketones,25c the oxidation and subsequent hydrolysis of α-acetoxyacetylenes,25d or the oxidation of 3(2 H )-furanone 25e (Scheme ). α-Alkyl and α-( α-hydroxyalkyl)-benzotriazolyloxiranes of the type 5a , b , e , f have already been utilized for the synthesis of corresponding α-hydroxy ketones 18a. Similarly, treatment of α-acylbenzotriazolyloxiranes 5g , h with perchloric acid readily gave 3-hydroxy-1,2-diones 7a and 7b in 73 and 86% yield, respectively (Scheme ).…”
Section: Resultsmentioning
confidence: 99%
“…3-Hydroxy-1,3,3-triphenyl-1,2-propanedione ( 7a ) and 1-(1-hydroxycyclohexyl)-2-phenyl-1,2-ethanedione ( 7b ) were prepared according to the general procedure reported previously 18a…”
Section: Methodsmentioning
confidence: 99%
“…Benzotriazolyloxiranes have earlier been prepared by the epoxidation of 1-(1-alkenyl)benzotriazoles using m -CPBA18a and dimethyldioxirane 18b. The hydrolysis of α-alkyl- and α-(α-hydroxyalkyl)-benzotriazolyloxiranes gives the corresponding α-hydroxy ketones 18a.…”
Section: Introductionmentioning
confidence: 99%
“…Benzotriazolyloxiranes have earlier been prepared by the epoxidation of 1-(1-alkenyl)benzotriazoles using m -CPBA18a and dimethyldioxirane 18b. The hydrolysis of α-alkyl- and α-(α-hydroxyalkyl)-benzotriazolyloxiranes gives the corresponding α-hydroxy ketones 18a. We now report another convenient and general method for the preparation of benzotriazolyloxiranes and their further transformations to octa-1,7-dien-4-ols and 3-hydroxy-1,2-diones.…”
1-Benzotriazolylchloromethyllithium generated from 1-chloromethylbenzotriazole (1) and LDA reacts with enolizable and nonenolizable ketones to give benzotriazolyloxiranes 2a-g in good yields. The oxiranyllithiums 4a-d generated from 2a-d and n-BuLi at -78 degrees C were trapped by a variety of electrophiles to give oxiranyl derivatives 5a-j in good to excellent yields. Lewis-acid-promoted nucleophilic ring opening of benzotriazolyloxiranes 2a,f,g with allyltrimethylsilane gave the corresponding 1,7-octadien-4-ols 6a-c in 68-75% yield. Hydrolysis of alpha-acylbenzotriazolyloxiranes 5g,h provided 3-hydroxy-1,2-diones 7a and 7b in 73 and 86% yield, respectively.
“…Stereochemistry of the molecule is preserved during these transformations. Significant stabilization of the oxirane ring by the benzotriazolyl substituent makes its opening difficult; thus, heating in 3 N sulfuric acid was required to convert oxirane 767 into hydroxyketone 769 <2001ARK(v)68> . Scheme 120 …”
Section: Reactivity Of Substituents Attached To Ring Nitrogensmentioning
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