Regiospecific C–N Photocyclization of 2-Styrylquinolines

Gulakova, E. N.; Berdnikova, Daria V.; Aliyeu, Tseimur M.; Fedorov, Yuri V.; Godovikov, Ivan A.; Федорова, О. А.

doi:10.1021/jo500696n

Cited by 34 publications

(18 citation statements)

References 33 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[6] Monochromophoric 2SQ itself undergoes only transcis photoisomerization, [7] albeit entering electron-donor substituents into the styryl group promotes photocyclization. [8] The same effect, i. e. promotion of photocyclization, has a benzene ring annealing to quinoline nucleus. The angular annelation gives 3-styrylbenzo[f]quinoline (SBQ), whose de-rivatives (substituted in the styryl group) are able to the CÀN photocyclization.…”

Section: Introductionmentioning

confidence: 97%

“…It has been stated recently that the bichromophoric dyad with two 2‐styrylquinoline (2SQ) chromophores connected by an ortho ‐xylylene bridge undergoes [2+2] photocycloaddition with quantitative formation of a single rctt cyclobutane derivative . Monochromophoric 2SQ itself undergoes only trans ‐ cis photoisomerization, albeit entering electron‐donor substituents into the styryl group promotes photocyclization …”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Interchromophore [2+2]photocycloaddition vs. intrachromophore C‐N photocyclization in bis–styrylbenzoquinoline dyad

2016

View full text Add to dashboard Cite

Photophysical and photochemical properties of a novel bichromophoric dyad (EE‐D), where two 3‐styrylbenzo[f]quinoline chromophoric groups (trans‐isomers) are connected by an ortho‐xylylene group, in comparison with the model compound trans‐3‐(3‐methoxystyryl)benzo[f]quinoline (E‐MSBQ), are investigated. The main photochemical reaction of the E‐MSBQ is trans → cis photoisomerization with subsequent intrachromophoric C−N photocyclization and oxidation to a derivative of 12b‐azonia‐benzo[c]chrysene (ABC). In contrast to the E‐MSBQ, upon irradiation of the EE‐D, in addition to photoisomerization, interchromophoric [2+2]photocycloaddition takes place and results in formation of a cyclobutane (CB) derivative. Due to reversibility of photoisomerization, under irradiation, both the E‐MSBQ and the EE‐D can be completely transformed to the ABC and CB derivatives, respectively. DFT calculations taking into account dispersion interactions (hybrid functional M06‐2X) allow explanation of the effective stereospecific [2+2]photocycloaddition in the dyad EE‐D by π‐stacking that orients two SBQ groups head‐to‐head and promotes formation of a single CB isomer.

show abstract

Section: Introductionmentioning

confidence: 97%

Section: Introductionmentioning

confidence: 99%

Interchromophore [2+2]photocycloaddition vs. intrachromophore C‐N photocyclization in bis–styrylbenzoquinoline dyad

2016

View full text Add to dashboard Cite

show abstract

“…Berdnikova and co-workers have developed a photochemical method to convert 2-styrylquinolines into quinolino[1,2-a]quinolinium derivatives (Scheme 52). 52 Irradiation of an acetonitrile solution of the starting material with a 125 W immersed mercury lamp initiated an E/Z isomerization and subsequent electrocyclization. Oxidative aromatization completed the cyclization, and addition of HClO 4 allowed for isolation of the perchlorate salt.…”

Section: Scheme 50 Photochemical Cascade For the Preparation Of Tetramentioning

confidence: 99%

Photochemical Synthesis of Azaheterocycles

Tanoury

2016

Synthesis

View full text Add to dashboard Cite

Synthetic organic photochemistry is a field that continues to offer unique routes to organic structures not typically accessed from thermal reactions. In this review, the photochemical synthesis of five-, six-, seven-, and eight-membered-ring azaheterocycles, as well as some aza-macrocycles, is discussed. The discussion will focus on methods where heterocycle formation occurs during or as a result of a photochemical event. Reaction mechanisms will be discussed also, as these provide a rationale for understanding the synthetic results. 1 Introduction 2 Five-Membered Rings 2.1 Cyclization Reactions 2.2 Cycloadditions 2.3 From Aromatic and Vinyl Azides 2.4 earrangements 2.5 Other Individual Methods 3 Six-Membered Rings 3.1 Cyclization Reactions 3.2 Isocyanide Insertions 3.3 Cycloadditions 4 Seven-Membered Rings and Larger 5 Conclusion Key words azaheterocycles, photocycloaddition, photocyclization, photorearrangement, photocatalyst Dr. Tanoury began his career in the pharmaceutical industry in 1992 as a Medicinal Chemist at the Burroughs-Wellcome Company in North Carolina. In 1996, he moved to Sepracor, Inc. in Massachusetts to start a career as a process development chemist. He moved to Vertex Pharmaceuticals in 2001 where he is currently a Senior Scientific Fellow in the Process Chemistry Department. Prior to starting his industrial career, Dr. Tanoury was a graduate student under the direction of Professor Barry M. Trost, earning his Ph.D. from Stanford University in 1989. This was followed by a National Institutes of Health postdoctoral fellowship at Harvard University from 1989-1992 in the labs of Professor E. J. Corey. In addition to synthetic organic chemistry and developing chemical processes for the manufacture of API, Dr. Tanoury's interests include understanding and probing chemical reactions using state-ofthe-art technology, and studying reaction mechanisms and chemical properties (ground and excited state) using theoretical/computational methods.

show abstract

“…We are developing regiospecific C–N photocyclization of hetarylphenylethenes resulting in the formation of charged polycyclic heteroaromatics. − In this reaction, a new C–N bond is formed through the photoinduced electrocyclic ring closure followed by in situ oxidation of the resulting dihydrohetarene intermediate by air oxygen. The process takes place under mild conditions at room temperature, does not require the use of catalysts, and allows to obtain fused polycyclic cations with good yields.…”

Section: Introductionmentioning

confidence: 99%

“…The process takes place under mild conditions at room temperature, does not require the use of catalysts, and allows to obtain fused polycyclic cations with good yields. Recently, we have shown that the C–N photocyclization of 2-styrylpyridine and 2-styrylquinolines leads to the efficient and selective formation of benzo[ c ]quinolizinium derivatives. Notably, we performed the photogeneration of the DNA-binding 8,9-dimethoxybenzo[ c ]quinolizinium derivative 6 as a key process in a five-component supramolecular cascade.…”

Section: Introductionmentioning

confidence: 99%

Regiospecific Photocyclization of Mono- and Bis-Styryl-Substituted N-Heterocycles: A Synthesis of DNA-Binding Benzo[c]quinolizinium Derivatives

et al. 2016

Self Cite

View full text Add to dashboard Cite

Regiospecific C-N photocyclization of mono- and bis-styryl-substituted N-heterocycles was investigated. We demonstrated that the C-N regiospecificity of the photoinduced electrocyclization is a general feature of ortho-styryl-substituted N-heterocycles comprising one and two nitrogen atoms. This phototransformation provides a straightforward synthesis of the pharmaceutically important benzo[c]quinolizinium cation and its aza-analogues. Noticeably, bis-styryl derivatives undergo only one-fold cyclization with the second styryl fragment remaining uninvolved in the cyclization process. Photocyclization products of monostyryl derivativatives intercalate into calf thymus DNA (ct DNA), whereas photocyclization products of bis-styryl derivativatives possess a mixed binding mechanism with ct DNA. The results can be used for development of novel DNA-targeting chemotherapeutics based on benzo[c]quinolizinium derivatives.

show abstract

Regiospecific C–N Photocyclization of 2-Styrylquinolines

Cited by 34 publications

References 33 publications

Interchromophore [2+2]photocycloaddition vs. intrachromophore C‐N photocyclization in bis–styrylbenzoquinoline dyad

Interchromophore [2+2]photocycloaddition vs. intrachromophore C‐N photocyclization in bis–styrylbenzoquinoline dyad

Photochemical Synthesis of Azaheterocycles

Regiospecific Photocyclization of Mono- and Bis-Styryl-Substituted N-Heterocycles: A Synthesis of DNA-Binding Benzo[c]quinolizinium Derivatives

Contact Info

Product

Resources

About