General and convenient route to alkenylidenecyclopropanes: generation of alkenylidenecarbenes from 1,1-dibromocyclopropanes under phase-transfer conditions

Isagawa, Kakuzo; Mizuno, Kazuhiko; Sugita, Hikaru; Otsuji, Yoshio

doi:10.1039/p19910002283

Cited by 65 publications

(15 citation statements)

References 9 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…1 H NMR spectrum, δ, ppm (J, Hz): 4.20 (1H, d, J = 12.4, CH 2 ); 4.65 (1H, d, J = 12.4, CH 2 ); 5.04 (1H, s, CH); 6.38-7.60 (29H, m, H arom ). 13 C NMR spectrum, δ, ppm: 53.0 (C-5), 65.7 (C-2), 111.9, 116. 8 …”

Section: -(4-chlorophenyl)-34-bis(diphenylmethylene)-1-phenylpyrrolmentioning

confidence: 99%

“…C NMR spectrum, δ, Chlorophenyl)-4-diphenylmethylene-1-phenyl-3-[(E)-1-phenylethylidene]pyrrolidine (3g) was prepared similarly to compound 3a from the vinylidenecyclopropane 1c and imine 2b in 24% yield with mp 169-170ºC (methanol). 1 H NMR spectrum, δ, ppm (J, Hz): 2.10 (3H, s, CH 3 ); 4.08 (1H, d, J = 11.6, CH 2 ); 4.48 (1H, d, J = 11.6, CH 2 ); 5.49 (1H, s, CH); 6.16 (2H, d, J = 7.3, H arom ); 6.53-6.83 (7H, m, H arom ); 6.84-7.10 (6H, m, H arom ); 7.13-7.50 (9H, m, H arom ) 13. C NMR spectrum, δ, ppm: 22.6 (CH 3 ); 53.2 (C-5); 65.0 (C-2); 111.9, 117.0, 126.3, 126.5, 127.91, 127.93, 128.1, 128.2, 128.4, 128.5, 128.8, 129.3, 129.5, 129.6, 129.8, 132.0, 133.3, 135.4, 139.8, 141.6, 142.1, 143.2, 143.4, 146.5.…”

mentioning

confidence: 99%

“…1 H NMR spectrum, δ, ppm (J, Hz): 2.14 (3H, s, CH 3 ); 4.11 (1H, d, J = 11.6, CH 2 ); 4.52 (1H, d, J = 11.6, CH 2 ); 5.55 (1H, s, CH); 6.18 (2H, d, J = 6.5, H arom ); 6.58-7.55 (23H, m, H arom ) 13. C NMR spectrum, δ, Chlorophenyl)-4-diphenylmethylene-1-phenyl-3-[(E)-1-phenylethylidene]pyrrolidine (3g) was prepared similarly to compound 3a from the vinylidenecyclopropane 1c and imine 2b in 24% yield with mp 169-170ºC (methanol).…”

mentioning

confidence: 99%

See 2 more Smart Citations

Synthesis of substituted pyrrolidines by reaction of aryl-substituted vinylidenecyclopropanes with aromatic imines catalyzed by BF3·Et2O

Stepakov

Larina

Radina

et al. 2008

Chem Heterocycl Comp

View full text Add to dashboard Cite

Vinylidenecyclopropanes have value as synthons in organic synthesis, in particular in the preparation of heterocyclic compounds [1][2][3][4][5][6]. Catalysis by Lewis acids has recently been reported in the reaction of vinylidenecyclopropanes with acetals to give indene derivatives [7]. It has previously been shown that the reaction of vinylidenecyclopropanes with aromatic imines or ethyl (arylimino)acetates in the presence of a Lewis acids gives pyrrolidine or 1,2,3,4-tetrahydroquinoline derivatives depending on the nature of the substituent on the multiple bond or in the cyclopropane ring [8,9]. We have found that the reaction of aromatic imines with vinylidenecyclopropanes containing alkyl substituents in the cyclopropane ring and on the multiple bond gives only the formation of products which occurs via a cyclopropyl-allyl rearrangement stage, i.e. substituted pyrrolidines. Vinylidenecyclopropanes containing an aryl and alkyl substituent simultaneously in the cyclopropane ring and aryl substituents on the double bond gave products the formation of which occurs via an intramolecular Friedel-Crafts reaction stage, i.e. tetrahydroquinoline derivatives [8]. Vinylidene-cyclopropanes containing two aryl substituents in the cyclopropane ring have not been included in this reaction hence the aim of this work was a study of the reaction of vinylidenecyclopropanes containing aryl substituents in the cyclopropane ring and on the double bond with aromatic imines in the presence of BF 3 ·Et 2 O.It was found that treating the 1,1-diaryl-2-(diphenylvinylidene)cyclopropanes 1a,b with the imines 2a,b in the presence of BF 3 ·Et 2 O (15 mol %) in methylene chloride gave the 2-aryl-4-diarylmethylene-3-diphenylmethylene-1-phenylpyrrolidines 3a-d in yields up to 27%. In all cases the target compounds were separated using preparative TLC. The structure and composition of compounds 3a-d were established from their spectroscopic and elemental analytical data. The 1 H NMR spectra of these compounds show doublet signals for the methylene group protons at 4.2 and 4.6 ppm (J = 12 Hz) and a methine proton singlet at 5.0 ppm assigned to the pyrrolidine ring. The 13 C NMR spectra show the signals for atoms C-2 and C-5 of the pyrrolidine ring at 66 and 53 ppm respectively. _________________________________________________________________________________________St.

show abstract

Section: -(4-chlorophenyl)-34-bis(diphenylmethylene)-1-phenylpyrrolmentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

See 1 more Smart Citation

Synthesis of substituted pyrrolidines by reaction of aryl-substituted vinylidenecyclopropanes with aromatic imines catalyzed by BF3·Et2O

Stepakov

Larina

Radina

et al. 2008

Chem Heterocycl Comp

View full text Add to dashboard Cite

show abstract

“…In past decades, the main body of investigations reported in the literature has been performed to understand the mechanism of the target bond cleavage in methylenecyclopropanes 1–3. At the same time, much less is known on vinylidenecyclopropanes although they represent the next nearest‐neighbor homologous members of these unsaturated hydrocarbons 4, 5.…”

Section: Introductionmentioning

confidence: 99%

Editorial Consultants—2003

2003

Cathet Cardio Intervent

View full text Add to dashboard Cite

“…In past decades, the main body of investigations reported in the literature has been performed to understand the mechanism of the target bond cleavage in meth-ylenecyclopropanes [1][2][3]. At the same time, much less is known on vinylidenecyclopropanes although they represent the next nearest-neighbor homologous members of these unsaturated hydrocarbons [4,5].…”

mentioning

confidence: 99%

C₁C₂ bond cleavage in vinylidenecyclopropanes: Theoretical density functional theory study

Zhanpeisov

Mizuno

Anpo

et al. 2003

Int J of Quantum Chemistry

Self Cite

View full text Add to dashboard Cite

ABSTRACT:Density functional calculations at the B3LYP/6-31G* level were carried out to investigate the photo rearrangements in 1,1-diarylvinylidene-2,3-dimethyl-and 1,1-diarylvinylidene-2,2,3,3-tetramethylcyclopropanes. Among the five different routes considered, none except the one leading to the final products of butatriene derivatives (route 4) was found to be able to explain the experimental findings only. However, the route 4 points out on the involvement of the C 1 OC 2 bond cleavage in strained cyclopropane ring. Thus, a new mechanism that results in successive transformations was suggested to explain this distinct C 1 OC 2 bond cleavage in cyclopropane ring for both precursors leading to formation of butatriene derivatives. The results of calculations indicate that photochemistry of vinylidenecyclopropane derivatives is significantly different than in the case of methylenecyclopropane compounds.

show abstract

General and convenient route to alkenylidenecyclopropanes: generation of alkenylidenecarbenes from 1,1-dibromocyclopropanes under phase-transfer conditions

Cited by 65 publications

References 9 publications

Synthesis of substituted pyrrolidines by reaction of aryl-substituted vinylidenecyclopropanes with aromatic imines catalyzed by BF3·Et2O

Synthesis of substituted pyrrolidines by reaction of aryl-substituted vinylidenecyclopropanes with aromatic imines catalyzed by BF3·Et2O

Editorial Consultants—2003

C₁C₂ bond cleavage in vinylidenecyclopropanes: Theoretical density functional theory study

Contact Info

Product

Resources

About

General and convenient route to alkenylidenecyclopropanes: generation of alkenylidenecarbenes from 1,1-dibromocyclopropanes under phase-transfer conditions

Cited by 65 publications

References 9 publications

Synthesis of substituted pyrrolidines by reaction of aryl-substituted vinylidenecyclopropanes with aromatic imines catalyzed by BF3·Et2O

Synthesis of substituted pyrrolidines by reaction of aryl-substituted vinylidenecyclopropanes with aromatic imines catalyzed by BF3·Et2O

Editorial Consultants—2003

C1C2 bond cleavage in vinylidenecyclopropanes: Theoretical density functional theory study

Contact Info

Product

Resources

About

C₁C₂ bond cleavage in vinylidenecyclopropanes: Theoretical density functional theory study