Direct Olefination of Fluorinated Benzothiadiazoles: A New Entry to Optoelectronic Materials

Zhang, Bo; He, Chun‐Yang; Zhang, Xingang

doi:10.1002/chem.201400075

Cited by 19 publications

(10 citation statements)

References 80 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[ 21 ] As described in Figure 1B, the styrene block as a conjugated bridge was integrated with the strong electron donor N , N ‐dimethylamino group to produce BTD‐710, whose absorption exhibited approximately 15 nm of redshift while emission in toluene (Tol) and dichloromethane (DCM) redshifted 30–90 nm relative to the reported BTD‐624 containing electron donor diarylamine. [ 22 ] Therefore, it is evident that the styrene bridge containing a N , N ‐dimethylamino electron donor is an ideal component for developing NIR fluorescent dyes.…”

Section: Resultsmentioning

confidence: 99%

Near‐Infrared Fluorescence/Photoacoustic Agent with an Intensifying Optical Performance for Imaging‐Guided Effective Photothermal Therapy

Huang

et al. 2020

Advanced Therapeutics

View full text Add to dashboard Cite

Near-infrared fluorescent agents generally exhibit typical push-pull electron characteristics, and their optical behaviors are closely related to their molecular structures. Benzobisthiadiazole moiety as a classic electron acceptor has been typically used to design the Donor-Acceptor-Donor (D-AD) type of fluorescent/photoacoustic agents with emission in the second near-infrared window. In this work, two strategies are examined to intensify their absorption/fluorescence and fluorescence/photoacoustic imaging performance: 1) the conjugated bridges are amplified by installing two electron-rich thiophenes and one styrene on two sides of the benzobisthiadiazole core and 2) the N,N-dimethylamino group is employed to replace the traditional diphenylamine to strengthen the electron donor. This agent shows the maximum absorption and fluorescence emission at 942 and 1302 nm, respectively. Its superior in vitro and vivo data confirms that the nanoparticles of this compound complexed with 1,2-distearoyl-sn-glycero-3phosphoethanolamine-N-[methoxy(polyethyleneglycol)] (DSPE-PEG) can not only perform real-time and high-contrast noninvasive near-infrared fluorescence/photoacoustic imaging of tumors (980 nm laser irradiation) but also effectively ablate the tumor cells by photothermal therapy implementing the dual-modality imaging method. In particular, its longer wavelength absorption and emission successfully improves the fluorescence/ photoacoustic imaging performance. These observations highlight its potential to be used as a promising therapeutic platform for cancer.

show abstract

Section: Resultsmentioning

confidence: 99%

Near‐Infrared Fluorescence/Photoacoustic Agent with an Intensifying Optical Performance for Imaging‐Guided Effective Photothermal Therapy

Huang

et al. 2020

Advanced Therapeutics

View full text Add to dashboard Cite

show abstract

“…Differentially substituted BT and BTz derivatives have also been obtained by Zhang and coworkers via selective direct arylation of monobromo BT with aryl iodides or by direct arylation of using an ~3-fold excess of acceptor to the aryl iodide [ 23 ]. Zhang and coworkers also reported the direct olefination of BT derivatives with Pd(OAc) 2 using silver(I) acetate and benzoquinone as co-oxidants to produce a variety of fluorescent compounds [ 24 ].…”

Section: Direct Arylation Of Electron-poor π-Conjugated Small Molementioning

confidence: 99%

Recent Developments in C–H Activation for Materials Science in the Center for Selective C–H Activation

et al. 2018

View full text Add to dashboard Cite

Organic electronics is a rapidly growing field driven in large part by the synthesis of π-conjugated molecules and polymers. Traditional aryl cross-coupling reactions such as the Stille and Suzuki have been used extensively in the synthesis of π-conjugated molecules and polymers, but the synthesis of intermediates necessary for traditional cross-couplings can include multiple steps with toxic and hazardous reagents. Direct arylation through C–H bond activation has the potential to reduce the number of steps and hazards while being more atom-economical. Within the Center for Selective C–H Functionalization (CCHF), we have been developing C–H activation methodology for the synthesis of π-conjugated materials of interest, including direct arylation of difficult-to-functionalize electron acceptor intermediates and living polymerization of π-conjugated polymers through C–H activation.

show abstract

“…Furthermore, a competitive reaction between electron-deficient and electron-rich alkenes with pentafluorobenzene was conducted, which provided their corresponding products in an almost 1:1 ratio, suggesting that the direct olefination of polyfluoroarenes has no bias on the nature of alkenes under these reaction conditions [89]. By a similar strategy, a series of olefin-containing fluorinated benzothiadiazoles were synthesized from fluorinated benzothiadiazoles in the presence of 2.5 mol% Pd(TFA)2, 3.0 equiv AgOAc, 2.5 equiv PhCO2H, and 0.1 equiv benzoquinone [90]. The reactions proceeded under mild conditions and showed good functional group compatibility.…”

Section: Fluorinated Aryl Halides or Pseudo-halides As The Coupling Amentioning

confidence: 99%

“…The reactions proceeded under mild conditions and showed good functional group compatibility. The products found important By a similar strategy, a series of olefin-containing fluorinated benzothiadiazoles were synthesized from fluorinated benzothiadiazoles in the presence of 2.5 mol% Pd(TFA) 2 , 3.0 equiv AgOAc, 2.5 equiv PhCO 2 H, and 0.1 equiv benzoquinone [90]. The reactions proceeded under mild conditions and showed good functional group compatibility.…”

Section: Fluorinated Aryl Halides or Pseudo-halides As The Coupling Amentioning

confidence: 99%

Pd-Catalyzed Mizoroki-Heck Reactions Using Fluorine-Containing Agents as the Cross-Coupling Partners

Yang

Zhao

et al. 2018

Catalysts

View full text Add to dashboard Cite

Abstract:The Mizoroki-Heck reaction represents one of the most convenient methods for carbon-carbon double bond formation in the synthesis of small organic molecules, natural products, pharmaceuticals, agrochemicals, and functional materials. Fluorine-containing organic compounds have found wide applications in the research areas of materials and life sciences over the past several decades. The incorporation of fluorine-containing segments into the target molecules by the Mizoroki-Heck reactions is highly attractive, as these reactions efficiently construct carbon-carbon double bonds bearing fluorinated functional groups by simple procedures. This review summarizes the palladium-catalyzed Mizoroki-Heck reactions using various fluorine-containing reagents as the cross-coupling partners. The first part of the review describes the Pd-catalyzed Mizoroki-Heck reactions of aryl halides or pseudo-halides with the fluorinated alkenes, and the second part discusses the Pd-catalyzed Mizoroki-Heck reactions of the fluorinated halides or pseudo-halides with alkenes. Variants of the Pd-catalyzed Mizoroki-Heck reactions with fluorine-containing reagents are also briefly depicted. This work supplies an overview, as well as a guide, to both younger and more established researchers in order to attract more attention and contributions in the realm of Mizoroki-Heck reactions with fluorine-containing participants.

show abstract

Direct Olefination of Fluorinated Benzothiadiazoles: A New Entry to Optoelectronic Materials

Cited by 19 publications

References 80 publications

Near‐Infrared Fluorescence/Photoacoustic Agent with an Intensifying Optical Performance for Imaging‐Guided Effective Photothermal Therapy

Near‐Infrared Fluorescence/Photoacoustic Agent with an Intensifying Optical Performance for Imaging‐Guided Effective Photothermal Therapy

Recent Developments in C–H Activation for Materials Science in the Center for Selective C–H Activation

Pd-Catalyzed Mizoroki-Heck Reactions Using Fluorine-Containing Agents as the Cross-Coupling Partners

Contact Info

Product

Resources

About