One-pot enyne metathesis/Diels–Alder/oxidation to six-membered silacycles with a multi-ring core: discovery of novel fluorophores

Yoshioka, Shohei; Fujii, Yuki; Tsujino, Hirofumi; Uno, Tadayuki; Fujioka, Hiromichi; Arisawa, Mitsuhiro

doi:10.1039/c7cc02788e

Cited by 14 publications

(11 citation statements)

References 45 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In our search for a novel and efficient ruthenium-catalyzed one-pot reaction involving both metathesis and nonmetathesis reactions, , we previously developed a one-pot ring-closing metathesis (RCM)/oxidation/1,3-dipolar cycloaddition protocol to prepare various isoindolo[2,1- a ]quinolines 3 from N -allyl-2-alkenylaniline derivatives 1 (Scheme ). The key intermediate in this reaction is likely to be azomethine ylide I derived from 1,2-dihydroquinoline 2 .…”

Section: Introductionmentioning

confidence: 99%

Metal-Free Nitrogen-Containing Polyheterocyclic Near-Infrared (NIR) Absorption Dyes: Synthesis, Absorption Properties, and Theoretical Calculation of Substituted 5-Methylisoindolo[2,1-a]quinolines

et al. 2019

Self Cite

View full text Add to dashboard Cite

We have synthesized and theoretically calculated 5-methylisoindolo[2,1- a ]quinoline derivatives as novel near-infrared absorption dyes via a ruthenium-catalyzed one-pot metathesis/oxidation/1,3-dipolar cycloaddition protocol. The reactivity in 1,3-dipolar cycloaddition was governed by the electronic effect of aromatic ring substituents. Substrates with an electron-withdrawing group on the aromatic ring afforded higher yields. The maximal absorption wavelength of 3,5-dimethyl-11-phenylisoindolo[2,1- a ]quinoline-7,10-dione and 11-(4-methoxyphenyl)-5-methylisoindolo[2,1- a ]quinoline-7,10-dione in MeOH increased to 736 and 737 nm, although that of 3a was 727 nm.

show abstract

Section: Introductionmentioning

confidence: 99%

Metal-Free Nitrogen-Containing Polyheterocyclic Near-Infrared (NIR) Absorption Dyes: Synthesis, Absorption Properties, and Theoretical Calculation of Substituted 5-Methylisoindolo[2,1-a]quinolines

et al. 2019

Self Cite

View full text Add to dashboard Cite

show abstract

“…Importantly, no significant difference was observed between 2 c and 2 k in terms of either the HOMO and LUMO orbitals or the HOMO–LUMO energy gaps (Figures S11b, S11e, and S11f). Therefore, the observed efficient fluorescence properties, especially in the solid state, may not arise from the electronic nature of silicon …”

Section: Resultsmentioning

confidence: 99%

“…Therefore, the observed efficient fluorescencep roperties, especially in the solid state, may not arise from the electronic nature of silicon. [30] Single-crystal X-ray structure determination was performed for 2a and 2c-e,a nd their packings tructures are shown in Figures 5-8. [20] These compounds 2a and 2c-e have nearly planar conformations, with dihedral angles (between two double bonds) of 3.50-11.48 (Figures S15, S16b, S18, and S21).…”

Section: Resultsmentioning

confidence: 99%

Rhodium‐Catalyzed Cascade Synthesis of Benzofuranylmethylidene‐Benzoxasiloles: Elucidating Reaction Mechanism and Efficient Solid‐State Fluorescence

Namba

Hayashi

Kawauchi

et al. 2018

Chemistry A European J

View full text Add to dashboard Cite

A new synthetic route to highly fluorescent benzofuranylmethylidenebenzoxasiloles through cationic rhodium(I)/binap complex-catalyzed cascade cycloisomerization of bis(2-ethynylphenol)silanes has been developed involving 1,2-silicon and 1,3-carbon (alkyne) migrations followed by oxycyclization. The present synthesis requires only three steps, starting from commercially available dichlorodiisopropylsilane, which is markedly shorter than our previous synthesis (eight steps starting from commercially available chlorodiisopropylsilane). Theoretical calculations elucidated the mechanism of the above cascade cycloisomerization. This reaction is initiated by the formation of a rhodium vinylidene not through direct 1,2-silicon migration but rather through an unprecedented stepwise 1,5-silicon migration followed by C-Si bond-forming cyclization from a dearomatized allenylrhodium complex. Subsequent 1,3-carbon (alkyne) migration leading to a η -allenyl/propargyl-rhodium complex followed by oxycyclization through π-bond (alkyne) activation with the cationic rhodium(I) complex affords the benzofuranylmethylidenebenzoxasilole product. The structure-fluorescence property relationships of the thus obtained benzofuranylmethylidenebenzoxasiloles were investigated, which revealed that good fluorescence quantum yields were generated in the solution state (φ =69-87 %) by introduction of electron-donating alkyl and phenyl groups on two phenoxy groups. In the powder state, 4-methyl- and 4-methoxy-phenoxy derivatives exhibited efficient blue fluorescence (φ =52 % and 46 %, respectively). Especially, the 4-methylphenoxy derivative was thermally stable, and exhibited strong narrow-band fluorescence in the film state (blue, φ =95 %) and redshifted strong narrow-band fluorescence (green, φ =90 %) in the crystalline state as a result of the formation of an offset π-stacked dimer; the latter was confirmed by X-ray crystallographic analysis and by theoretical calculations.

show abstract

“…Recently, we have developed a one-pot enyne metathesis/Diels–Alder reaction/oxidation methodology to yield six-membered silacycles that contain multiple rings (Scheme ). We considered that the key intermediates 1 and 3 in the above one-pot reactions and the isomer of 1 , 2 might offer further examples of multiple Diels–Alder reaction.…”

Section: Introductionmentioning

confidence: 99%

Cascade Multiple Diels–Alder Reactions of Styrene Derivatives with Maleimide or Maleic Anhydride

et al. 2018

Self Cite

View full text Add to dashboard Cite

show abstract

One-pot enyne metathesis/Diels–Alder/oxidation to six-membered silacycles with a multi-ring core: discovery of novel fluorophores

Cited by 14 publications

References 45 publications

Metal-Free Nitrogen-Containing Polyheterocyclic Near-Infrared (NIR) Absorption Dyes: Synthesis, Absorption Properties, and Theoretical Calculation of Substituted 5-Methylisoindolo[2,1-a]quinolines

Metal-Free Nitrogen-Containing Polyheterocyclic Near-Infrared (NIR) Absorption Dyes: Synthesis, Absorption Properties, and Theoretical Calculation of Substituted 5-Methylisoindolo[2,1-a]quinolines

Rhodium‐Catalyzed Cascade Synthesis of Benzofuranylmethylidene‐Benzoxasiloles: Elucidating Reaction Mechanism and Efficient Solid‐State Fluorescence

Cascade Multiple Diels–Alder Reactions of Styrene Derivatives with Maleimide or Maleic Anhydride

Contact Info

Product

Resources

About