Transannular reactions of cycloalkenes, cycloalkadienes, and cycloalkatrienes. 17. N-Heterocyclization in electrophilic haloamidation reactions of 1,5-cyclooctadiene. Synthesis and rearrangements of the granatanine and homonortropane skeletons

Haufe, Guenter; Rolle, U.; Kleinpeter, Erich; Kivikoski, J.; Rissanen, Kari

doi:10.1021/jo00077a031

Cited by 17 publications

(7 citation statements)

References 1 publication

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Below are given the results of our study on the reaction of an isolated diene, cycloocta-1,5-diene (1,5-COD), with trifluoromethanesulfonamide in the oxidative system t-BuOClNaI · 2 H 2 O. Cycloocta-1,5-diene is known not only as ligand for complexation with transition metals but also as important synthon for design of various carbo-and heterocycles. Electrophilic transannular addition to 1,5-COD could give rise to bicyclic compounds of three types, bicyclo[3.3.0]octanes [5], 9-heterobicyclo[3.3.1]-nonanes [6][7][8][9][10][11], or mixtures of the latter with isomeric 2,5-disubstituted 9-heterobicyclo[4.2.1]nonanes [12][13][14][15][16][17][18][19][20][21][22][23][24][25] (Scheme 3). We have found no published data on the synthesis of fluorinated azabicyclononanes from 1,5-COD.…”

mentioning

confidence: 99%

Reaction of trifluoromethanesulfonamide with alkenes and cycloocta-1,5-diene under oxidative conditions. Direct assembly of 9-heterobicyclo[4.2.1]nonanes

2011

View full text Add to dashboard Cite

Reactions of trifluoromethanesulfonamide with α-methylstyrene, 2-methylpent-1-ene, and cycloocta-1,5-diene in the system t-BuOCl-NaI were studied. In the reaction with α-methylstyrene 1-iodo-2-phenylpropan-2-ol was the only isolated product. The reaction with 2-methylpent-1-ene gave a mixture of N,N′-(2-methylpentane-1,2-diyl)bis(trifluoromethanesulfonamide), trifluoro-N-(2-hydroxy-2-methylpentyl)-methanesulfonamide, and N, N′-[oxybis(2-methylpentan-2,1-diyl)]bis(trifluoromethanesulfonamide). Trifluoromethanesulfonamide reacted with cycloocta-1,5-diene to produce a mixture of 2,5-diiodo-9-(trifluoromethylsulfonyl)-9-azabicyclo[4.2.1]nonane and 2,5-diiodo-9-oxabicyclo[4.2.1]nonane; this reaction may be regarded as the first example of direct assembly of bicyclononane skeleton.We recently showed that aziridination of styrene with trifluoromethanesulfonamide in the oxidative system t-BuOCl-NaI · 2 H 2 O leads to formation of both linear structures I and II and heterocyclization product, 2,5-diphenyl-1,4-bis(trifluoromethylsulfonyl)piperazine (III) [1]. The structure of III was proved by X-ray analysis, and a mechanism involving intermediate formation of 2-phenyl-1-trifluoromethylaziridine was proposed [1]. However, the formation of substituted piperazine instead of expected aziridine contradicted the data reported by Minakata et al. [2], according to which aziridines were obtained in reactions of styrene and other alkenes with sulfonamides under analogous conditions due to strong electron-withdrawing effect of the CF 3 group [1]. We tried to reproduce the conditions described in [2] more accurately and carried out the reaction of styrene with trifluoromethanesulfonamide in the presence of anhydrous sodium iodide. In this case, we isolated compounds I and II and 2,6-diphenyl-1,4-bis(trifluoromethylsulfonyl)piperazine (IV) which is isomeric to III [3].In the present work we studied reactions of trifluoromethanesulfonamide with α-methylstyrene, 2-methylpent-1-ene, and cycloocta-1,5-diene under oxidative conditions (in the presence of t-BuOCl-NaI or t-BuOCl-NaI · 2 H 2 O) and analyzed possible ways of formation of the corresponding products.Taking into account that α-methylstyrene reacted with trifluoromethanesulfonamide in a way similar to styrene [2], i.e., with formation of the corresponding aziridine, and that the reaction direction strongly depends on the composition of the oxidative system, α-methylstyrene (V) was brought into reaction with trifluoromethanesulfonamide in two systems containing NaI · 2H 2 O or anhydrous NaI (as in [2]). In both cases, the only product was 1-iodo-2-phenylpropan-2-ol (VI) (Scheme 1). Compound VI is likely to be formed via iodination of α-methylstyrene with t-BuOI to

show abstract

mentioning

confidence: 99%

Reaction of trifluoromethanesulfonamide with alkenes and cycloocta-1,5-diene under oxidative conditions. Direct assembly of 9-heterobicyclo[4.2.1]nonanes

2011

View full text Add to dashboard Cite

show abstract

“…Nitrogen analogues 3 were synthesized by a stepwise procedure that is more general than a previously reported route using N -halosuccinimide . Catalytic oxidation of 1,5-COD to cis -diepoxide 4 was followed by ring-opening with four different amines to provide 9-azabicyclo[3.3.1]- and [4.2.1]nonanediols 5a – d (Figure B).…”

Section: Resultsmentioning

confidence: 99%

Thia-, Aza-, and Selena[3.3.1]bicyclononane Dichlorides: Rates vs Internal Nucleophile in Anchimeric Assistance

et al. 2011

View full text Add to dashboard Cite

Sulfur-, selenium-, and nitrogen-containing compounds bearing leaving groups in the β-position undergo facile substitution chemistry enabled by anchimeric assistance. Here we provide direct comparisons between such systems in the rigid bicyclo[3.3.1]nonane framework easily derived from 1,5-cyclooctadiene. For a series of dichloride electrophiles of this type, the relative reactivities were found to be Se ≫ (alkyl)N > S ≥ (propargyl)N > (phenyl)N, with the reaction rates at the two extremes differing by more than 3 orders of magnitude. For the N-alkyl case, substitution rates were largely independent of the trapping nucleophile but were strongly dependent on solvent, showing that the process is controlled by the formation of the high-energy three-membered cationic intermediate.

show abstract

“…[10][11][12][13][14][15][16][17][18][19] Urea undergoes a variety of chemical reactions to afford wide range of important compounds. [32][33][34][35][36][37][38][39][40][41] Extensive investigations have recently been carried out for the preparation of libraries of urea compounds with potential biological activities. 31 Due to their broad spectrum applications, the synthesis of urea derivatives has received considerable attention.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Some Heterocycle Containing Urea Derivatives and Their Anti-viral Activity

Verma¹,

Singh²,

Clercq³

2006

HETEROCYCLES

View full text Add to dashboard Cite

Some new isoindol heterocyclic ureas (6a-6i) have been synthesized using N-aminophthalimide (2) and ethyl N-monosubstituted/ethyl N,Ndisubstituted carbamate (5a-5i). All the newly synthesized final compounds have been evaluated for their anti-viral activities against a variety of viruses.The compound (6f) with the methoxy substituent showed reasonably better activity as compared to the standard drugs against all the viruses (cf. Tables 1, 2 and 3). Further, all the products (6a-6i) were found to be active against Vesicular stomatitis virus, Coxsackie virus B4 and Respiratory syncytical virus (cf. Table 2) and the compounds (6h) and (6i) displayed better antiviral activity in comparison to Brivudin and (S)-DHPA (cf. Table 3).

show abstract

Transannular reactions of cycloalkenes, cycloalkadienes, and cycloalkatrienes. 17. N-Heterocyclization in electrophilic haloamidation reactions of 1,5-cyclooctadiene. Synthesis and rearrangements of the granatanine and homonortropane skeletons

Cited by 17 publications

References 1 publication

Reaction of trifluoromethanesulfonamide with alkenes and cycloocta-1,5-diene under oxidative conditions. Direct assembly of 9-heterobicyclo[4.2.1]nonanes

Reaction of trifluoromethanesulfonamide with alkenes and cycloocta-1,5-diene under oxidative conditions. Direct assembly of 9-heterobicyclo[4.2.1]nonanes

Thia-, Aza-, and Selena[3.3.1]bicyclononane Dichlorides: Rates vs Internal Nucleophile in Anchimeric Assistance

Synthesis of Some Heterocycle Containing Urea Derivatives and Their Anti-viral Activity

Contact Info

Product

Resources

About