- Efficient Far-Red/Near-IR Absorbing BODIPY Photocages by Blocking Unproductive Conical Intersections
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Photocages are light-sensitive chemical protecting groups that give investigators control over activation of biomolecules using targeted light irradiation. A compelling application of far-red/near-IR absorbing photocages is their potential for deep tissue activation of biomolecules and phototherapeutics. Toward this goal, we recently reported BODIPY photocages that absorb near-IR light. However, these photocages have reduced photorelease efficiencies compared to shorter-wavelength absorbing photocages, which has hindered their application. Because photochemistry is a zero-sum competition of rates, improvement of the quantum yield of a photoreaction can be achieved either by making the desired photoreaction more efficient or by hobbling competitive decay channels. This latter strategy of inhibiting unproductive decay channels was pursued to improve the release efficiency of long-wavelength absorbing BODIPY photocages by synthesizing structures that block access to unproductive singlet internal conversion conical intersections, which have recently been located for simple BODIPY structures from excited state dynamic simulations. This strategy led to the synthesis of new conformationally restrained boron-methylated BODIPY photocages that absorb light strongly around 700 nm. In the best case, a photocage was identified with an extinction coefficient of 124000 M-1 cm-1, a quantum yield of photorelease of 3.8%, and an overall quantum efficiency of 4650 M-1 cm-1 at 680 nm. This derivative has a quantum efficiency that is 50-fold higher than the best known BODIPY photocages absorbing >600 nm, validating the effectiveness of a strategy for designing efficient photoreactions by thwarting competitive excited state decay channels. Furthermore, 1,7-diaryl substitutions were found to improve the quantum yields of photorelease by excited state participation and blocking ion pair recombination by internal nucleophilic trapping. No cellular toxicity (trypan blue exclusion) was observed at 20 μM, and photoactivation was demonstrated in HeLa cells using red light.
- Shrestha, Pradeep,Dissanayake, Komadhie C.,Gehrmann, Elizabeth J.,Wijesooriya, Chamari S.,Mukhopadhyay, Atreyee,Smith, Emily A.,Winter, Arthur H.
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Read Online
- Linking of Alcohols with Vinyl Azides
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A protocol to link alcohols with vinyl azides has been established through fluoro- or bromo-alkoxylation of vinyl azides to provide α-alkoxy-β-haloalkyl azides. A series of primary and secondary alcohols including natural products and their derivatives such as sugars and steroids were successfully anchored with vinyl azides. The as-prepared cyanine dye linked testosterones were capable of rapid cell membrane imaging in real time.
- Wang, Yi-Feng,Hu, Ming,Hayashi, Hirohito,Xing, Bengang,Chiba, Shunsuke
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Read Online
- A General Method for the Dibromination of Vicinal sp3C-H Bonds Exploiting Weak Solvent-Substrate Noncovalent Interactions
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A general procedure of 1,2-dibromination of vicinal sp3 C-H bonds of arylethanes using N-bromosuccinimide as the bromide reagent without an external initiator has been established. The modulation of the strength of the intermolecular noncovalent interactions between the solvent and arylethane ethanes, quantitatively evaluated via quantum chemical calculations, allows us to circumvent the fact that arylethane ethane cannot be dibrominated through traditional methods. The mechanism was explored by both experiments and quantum chemical calculations, revealing a radical chain with HAA process.
- Qi, Zaojuan,Li, Weihe,Niu, Yanning,Benassi, Enrico,Qian, Bo
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supporting information
p. 2399 - 2404
(2021/03/03)
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- Photoredox-catalyzed synthesis of N-unsubstituted enaminosulfones from vinyl azides and sulfinates
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A metal-free visible light photoredox-catalyzed synthesis of N-unsubstituted enaminosulfones from vinyl azides and sodium sulfinates in moderate to high yields is described. The reaction proceeds in ethanol and uses eosin Y as a readily available photocatalyst in combination with nitrobenzene as an electron shuttle. Taking into account the number of steps involved (generation of the sulfonyl radical, its addition to the double bond, elimination of molecular nitrogen with formation of an iminyl radical, followed by its reduction and protonation) as well as the number of redox-active reaction partners involved, the selectivity of the process is quite impressive.
- Mulina, Olga M.,Ilovaisky, Alexey I.,Opatz, Till,Terent'ev, Alexander O.
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supporting information
(2021/01/11)
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- A general strategy to optimize the performance of aza-BODIPY-based probes for enhanced photoacoustic properties
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In this chapter, we describe a generalizable strategy to obtain a high PA output platform that is optimized for ratiometric imaging. Our approach entails conformationally restricting pendant aryl rings on the aza-BODIPY core to enhance orbital overlap which consequently increases the extinction coefficient. This strategy can potentially be applied to other dye platforms to enhance their signal intensity. We provide detailed protocols for the synthesis, in vitro characterization, and in vivo application.
- Yadav, Anuj K.,Tapia Hernandez, Rodrigo,Chan, Jefferson
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p. 415 - 441
(2021/07/26)
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- Electrosynthesis of N-unsubstituted enaminosulfones from vinyl azides and sodium sulfinates mediated by NH4I
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A wide range of N-unsubstituted enaminosulfones were obtained via electrochemical sulfonylation of vinyl azides with sulfonyl radicals generated from sodium sulfinates. The discovery of N-unsubstituted enaminosulfones synthesis is based on a unique ability of the azido group to eliminate the N2 molecule. The process is performed under constant current conditions in an experimentally convenient undivided electrochemical cell equipped with a graphite anode and a stainless steel cathode applying NH4I both as the redox catalyst and the supporting electrolyte.
- Mulina, Olga M.,Doronin, Mikhail M.,Terent'ev, Alexander O.
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supporting information
(2021/10/16)
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- An aryl thiol-vinyl azide coupling reaction and a thiol-vinyl azide coupling/cyclization cascade: efficient synthesis of β-ketosulfides and arene-fused 5-methylene-2-pyrrolidinone derivatives
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The addition reaction of thiol to vinyl azide has been extensively studied. Variously substituted aryl thiols are all viable for this coupling process. The scope of the other partner is successfully expanded from α-aryl vinyl azide to α-alkyl vinyl azide.
- Wang, Yong,Wang, Yu-Jiao,Liang, Xian-Chen,Shen, Mei-Hua,Xu, Hua-Dong,Xu, Defeng
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supporting information
p. 5169 - 5176
(2021/06/21)
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- Electrocatalytic Synthesis of gem -Bisarylthio Enamines and α-Phenylthio Ketones via a Radical Process under Mild Conditions
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The novel method for the synthesis of gem -bisarylthio enamines and α-phenylthio ketones was developed via the coupling of α-substituted vinyl azides with thiols in the presence of tetrabutylammonium iodide (TBAI) as a redox catalyst and electrolyte at ro
- Pan, Yong-Zhou,Cheng, Shi-Yan,Li, Qian-Yu,Tang, Hai-Tao,Pan, Ying-Ming,Meng, Xiu-Jin,Mo, Zu-Yu
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supporting information
p. 593 - 600
(2021/03/17)
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- Electrochemical Oxidative Cross-Coupling between Vinyl Azides and Thiophenols: Synthesis ofgem-Bisarylthio Enamines
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An electrochemical radical strategy involving alkene substrates provides a powerful approach for alkene functionalization. Herein, we described the first electrochemical synthesis ofgem-bisarylthio enamines from vinyl azides and thiophenols through the C-
- Li, Guodong,Yu, Ke,Yang, Jiajun,Xu, Bo,Chen, Qianjin
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p. 15946 - 15952
(2021/07/20)
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- Access to Cycloalkeno[ c]-Fused Pyridines via Pd-Catalyzed C(sp2)-H Activation and Cyclization of N-Acetyl Hydrazones of Acylcycloalkenes with Vinyl Azides
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A novel Pd(II)-catalyzed vinylic C-H activation and cyclization has been developed, reacting a series of small, medium, and large N-acetyl hydrazones of acylcycloalkenes with vinyl azides to access diverse cycloalkeno[c]-fused pyridine scaffolds. This protocol provides progress in C(sp2)-H bond activation of medium to large cycloalkenes, and the target products can be obtained in a specific regioselectivity with good functional group tolerance and a broad substrate scope.
- Nie, Biao,Wu, Wanqing,Ren, Qingyun,Wang, Zhongqing,Zhang, Ji,Zhang, Yingjun,Jiang, Huanfeng
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supporting information
p. 7786 - 7790
(2020/11/02)
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- Synthesis of Isoquinoline Derivatives via Palladium-Catalyzed C?H/C?N Bond Activation of N-Acyl Hydrazones with α-Substituted Vinyl Azides
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A palladium-catalyzed cyclization of N-acetyl hydrazones with vinyl azides has been developed. Various substituted isoquinolines, including diverse fused isoquinolines can be prepared via this protocol in moderate to good yields. Mechanistic studies suggest that α-substituted vinyl azide serves as an internal nitrogen source. Also, C?H bond activation and C?N bond cleavage have been realized using hydrazone as directing group. (Figure presented.).
- Jiang, Huanfeng,Nie, Biao,Ren, Qingyun,Wu, Wanqing,Zeng, Wei,Zhang, Ji,Zhang, Yingjun
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supporting information
(2020/02/25)
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- Electrochemically Induced Synthesis of Sulfonylated N-Unsubstituted Enamines from Vinyl Azides and Sulfonyl Hydrazides
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Sulfonylated N-unsubstituted enamines were synthesized through a chain of chemical and electrochemical transformations via sulfonylation of vinyl azides. The disclosing of the N-unsubstituted enamines synthesis was based on a unique property of the azido group, which is its ability to eliminate the N2 molecule. Furthermore, a formal paradox is observed: A double bond reacts and a double bond is retained. Electrosynthesis proceeded in an undivided cell equipped with a graphite anode and a stainless steel cathode; NH4I was used as a supporting electrolyte.
- Mulina, Olga M.,Zhironkina, Nataliya V.,Paveliev, Stanislav A.,Demchuk, Dmitry V.,Terent'Ev, Alexander O.
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supporting information
p. 1818 - 1824
(2020/03/04)
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- Self-Catalyzed Rapid Synthesis of N-Acylated/ N-Formylated α-Aminoketones and N-Hydroxymethylated Formamides from 3-Aryl-2 H-Azirines and 2-Me/Ph-3-Aryl-2 H-Azirines
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A rapid and effective method has been established for the synthesis of N-acylated α-aminoketone derivatives by the reaction of 3-aryl-2H-azirines and highly substituted 2-Me/Ph-3-aryl-2H-azirines with various carboxylic acids under ambient air within 10 min at room temperature. N-Trifluoroacetylated α-aminoketones with different substituents have been reported in the presence of trifluoroacetic acid. This protocol is equally effective to synthesize N-formylated α-aminoketone and N-hydroxymethylated formamide derivatives.
- De, Aramita,Majee, Adinath,Santra, Sougata,Zyryanov, Grigory V.
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p. 3926 - 3930
(2020/07/14)
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- Electrochemical Synthesis of O-Phthalimide Oximes from α-Azido Styrenes via Radical Sequence: Generation, Addition and Recombination of Imide-N-Oxyl and Iminyl Radicals with C?O/N?O Bonds Formation
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Electrochemically induced radical-initiated reaction of vinyl azides with N-hydroxyphthalimide resulting O-phthalimide oximes with challenging for organic chemistry N?O-N fragment has been discovered. The developed approach introduces in synthesis electrochemically generated O-centered imide-N-oxyl radicals as the coupling components. Sequential formation of C?O and N?O bonds was achieved via generation and selective addition of imide-N-oxyl radicals, followed by recombination with iminyl radicals. A wide range of O-phthalimide oximes was obtained with the yields up to 84percent. (Figure presented.).
- Paveliev, Stanislav A.,Churakov, Artem I.,Alimkhanova, Liliya S.,Segida, Oleg O.,Nikishin, Gennady I.,Terent'ev, Alexander O.
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supporting information
p. 3864 - 3871
(2020/07/30)
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- Mono-iodine substituted BODIPY compound and preparation method and application thereof
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The invention belongs to the field of drug synthesis, relates to a BODIPY compound shown as a general formula (I), in particular to a mono-iodine substituted BODIPY compound and a preparation method and application thereof in pharmacy. Tests show that the
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Paragraph 0042-0045
(2020/12/15)
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- AgN3-Catalyzed Hydroazidation of Terminal Alkynes and Mechanistic Studies
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The hydroazidation of alkynes is the most straightforward way to access vinyl azides-versatile building blocks in organic synthesis. We previously realized such a fundamental reaction of terminal alkynes using Ag2CO3 as a catalyst. H
- Bi, Xihe,Cao, Shanshan,Ji, Qinghe,Li, Huaizhi,Pang, Maolin,Yuan, Haiyan,Zhang, Jingping
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supporting information
p. 7083 - 7091
(2020/05/14)
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- Metal-Free Electrochemical Coupling of Vinyl Azides: Synthesis of Phenanthridines and β-Ketosulfones
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We reported an efficient and environmentally benign electrochemical synthesis of phenanthridines by oxidative coupling of vinyl azides with sodium azide or benzenesulfonyl hydrazides, for the first time. The reaction conditions are mild, and no additional metal-catalyst or exogenous oxidants are needed. The protocol has broad substrate scope and high functional group tolerance. Furthermore, this green electrochemical procedure can be readily extended to the synthesis of β-ketosulfones. Gram scale reactions further demonstrate the practicability.
- Chen, Qianjin,Kong, Xianqiang,Li, Guodong,Liang, Qi,Lin, Long,Xu, Bo,Yu, Ke
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supporting information
p. 6135 - 6145
(2020/10/06)
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- Indium(iii) catalyzed reactions of vinyl azides and indoles
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Indium trichloride catalyzes the reaction of vinyl azides with unfunctionalized indoles to give vinyl indoles. This is the first example of displacement of the azide group by a carbon nucleophile while preserving the vinyl function. The protocol employs very mild reaction conditions and offers excellent yields of diverse 3-vinyl indoles. It is amenable to gram scale. Access to a library of 3,3′-bis(indolyl)methanes through condensation of vinyl azides with 2 equiv of an indole is demonstrated.
- More, Atul A.,Szpilman, Alex M.
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supporting information
p. 3759 - 3764
(2020/06/08)
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- Highly Enantioselective Iridium-Catalyzed Coupling Reaction of Vinyl Azides and Racemic Allylic Carbonates
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The iridium-catalyzed enantioselective coupling reaction of vinyl azides and allylic electrophiles is presented and provides access to β-chiral carbonyl derivatives. Vinyl azides are used as acetamide enolate or acetonitrile carbanion surrogates, leading to γ,δ-unsaturated β-substituted amides as well as nitriles with excellent enantiomeric excess. These products are readily transformed into chiral N-containing building blocks and pharmaceuticals. A mechanism is proposed to rationalize the chemoselectivity of this coupling reaction.
- Han, Min,Yang, Min,Wu, Rui,Li, Yang,Jia, Tao,Gao, Yuanji,Ni, Hai-Liang,Hu, Ping,Wang, Bi-Qin,Cao, Peng
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p. 13398 - 13405
(2020/09/02)
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- Iridium-Catalyzed Enantioselective α-Allylic Alkylation of Amides Using Vinyl Azide as Amide Enolate Surrogate
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Among the unstabilized enolates used as nucleophiles in iridium-catalyzed asymmetric allylic alkylation reactions, amide enolates are the least explored. Vinyl azides are now employed as amide enolate surrogates in Ir-catalyzed asymmetric allylic alkylation with branched allylic alcohols as the allylic electrophile. Competing reaction pathways are suppressed through the systematic tuning of the steric and electronic properties of vinyl azide to effect the α-allylic alkylation of secondary acetamides with high atom economy, exclusive branched selectivity, and mostly excellent enantioselectivity.
- Chakrabarty, Aditya,Mukherjee, Santanu
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supporting information
p. 7752 - 7756
(2020/10/09)
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- Cerium(IV) ammonium nitrate promoted synthesis of O-phthalimide oximes from vinyl azides and N-hydroxyphthalimide
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O-Phthalimide oximes with an N–O–N fragment were synthesized in high yields via the reaction of vinyl azides with phthalimide-N-oxyl radicals derived from N-hydroxyphthalimide under the action of cerium(IV) ammonium nitrate. The disclosed process is based on the radical transformation of vinyl azides with the elimination of nitrogen and the formation of iminyl N-radicals. The developed approach exploited the dual reactivity of imide-N-oxyl radicals. They act as O-components for oxidative C–O coupling with vinyl azides and participate in subsequent formation of the N–O bond via their recombination with intermediate iminyl radicals.
- Paveliev, Stanislav A.,Alimkhanova, Liliya S.,Sergeeva, Anna V.,Terent'ev, Alexander O.
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supporting information
(2020/10/22)
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- Switchable reactivity between vinyl azides and terminal alkyne by nano copper catalysis
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A novel nano copper-catalyzed substrate-dependent chemodivergent transformation of vinyl azides with a terminal alkyne is disclosed. 2,5-Disubstituted pyrroles were selectively obtained in high yield with aryl alkynes and aliphatic alkynes, whereas 2,3,4-trisubstituted pyrroles were formed with silylated alkynes. This switchable method provides a controllable and facile access to both multisubstituted pyrrole scaffolds with high efficiency, excellent regioselectivity, and good functional group compatibility.
- Cen, Jinghe,Wu, Yaodan,Li, Jianxiao,Huang, Liangbin,Wu, Wanqing,Zhu, Zhongzhi,Yang, Shaorong,Jiang, Huanfeng
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supporting information
p. 2090 - 2094
(2019/03/26)
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- Visible-Light-Induced Regioselective C(sp3)-H Acyloxylation of Aryl-2 H-azirines with (Diacetoxy)iodobenzene
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A visible-light-promoted regioselective coupling of C(sp3)-H of aryl-2H-azirine and (diacetoxy)iodobenzene has been reported. Rose Bengal as an organophotoredox catalyst has been used in this reaction. The reaction proceeds under aerobic condition at room temperature. A variety of aryl-2H-azirines gives the corresponding acyloxylated azirines under this reaction conditions. The reaction goes through a radical pathway. The protocol is also applicable on gram-scale synthesis.
- De, Aramita,Santra, Sougata,Hajra, Alakananda,Zyryanov, Grigory V.,Majee, Adinath
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p. 11735 - 11740
(2019/10/02)
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- A Conformationally Restricted Aza-BODIPY Platform for Stimulus-Responsive Probes with Enhanced Photoacoustic Properties
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Photoacoustic (PA) dyes, which absorb near-infrared (NIR) light to generate an ultrasonic signal, can be detected at centimeter depths in tissues with significantly higher resolution than dyes imaged with fluorescence-based methods. As such, PA agents show great promise as research tools for the study of live-animal disease models. However, the development of activatable PA probes has been hampered by the relative scarcity of appropriate PA-active molecular platforms with properties that can be manipulated in a rational manner. Herein we synthesized and evaluated six modifications to the aza-BODIPY dye platform with respect to their absorbance, fluorescence, and PA properties. We identified a promising conformationally restricted aza-BODIPY (CRaB) scaffold that prioritizes three criteria necessary for the design of stimulus-responsive dyes with optimal ratiometric PA response: absorbance at NIR wavelengths, strong PA intensity, and large Δλ upon interaction with the desired stimulus. Using this scaffold, we synthesized three chemically diverse stimulus-responsive PA probes and demonstrated between 2- and 8-fold improvements in theoretical ratiometric response in vitro. This suggests that improvements in PA parameters are generalizable. Finally, we validated the in vitro turnover of each CRaB PA probe and demonstrated the in vivo potential of the CRaB scaffold by direct comparison to an established hypoxia-responsive probe for the detection of tumor hypoxia.
- Zhou, Effie Y.,Knox, Hailey J.,Liu, Chang,Zhao, Weili,Chan, Jefferson
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supporting information
p. 17601 - 17609
(2019/11/11)
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- Rhodium-Catalyzed Double Isocyanide Insertion via a Vinylcarbodiimide Intermediate for the Synthesis of 2H-Pyrrol-2-imines
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2 H -Pyrrol-2-imine is an important structural motif exhibiting in biologically active compounds and natural products. An efficient rhodium-catalyzed one-pot reaction of one vinyl azide with sequentially with two different isocyanides is reported, which offers an alternative facile access to 3-amino-5-aryl-2 H -pyrrol-2-imines bearing various substitution on the nitrogens in good yields. An unstable vinylcarbodiimide is the key intermediate in this cascade reaction.
- Li, Zongyang,Wang, Yunlong,Zhang, Zhenhua,Zhao, Haiying
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supporting information
p. 3250 - 3258
(2019/08/28)
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- Fluorine containing cyclopropanes: Synthesis of aryl substituted all-: cis 1,2,3-trifluorocyclopropanes, a facially polar motif
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The syntheses of substituted all-cis-1,2,3-trifluorocyclopropanes are described for the first time. The three fluorines located on each of the cyclopropyl carbons with a stereochemistry where they are all on the same face of the cyclopropane, imparts a significant polarity to the molecule, and the inherent conformational rigidity and lowering of logP makes this motif attractive for exploration as a substituent for pharmaceuticals and agrochemicals research.
- Fang, Zeguo,Cordes, David B.,Slawin, Alexandra M. Z.,O'hagan, David
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p. 10539 - 10542
(2019/09/06)
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- Direct access to bis-S-heterocycles via copper-catalyzed three component tandem cyclization using S8 as a sulfur source
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A novel strategy for constructing sulfur containing bis-S-heterocyclic compounds from oxime esters/vinyl azide, phenylacetylene/aldehydes and elemental sulfur (S8) has been developed. These transformations show good functional group tolerance. Various bis-S-heterocyclic products were efficiently synthesized from easily prepared or widely commercially available starting materials. In this protocol, S8 successfully served as a two-sulfur atom donor for thiophene and thiazole rings, respectively.
- Zhou, Peiqi,Huang, Yubing,Wu, Wanqing,Yu, Wentao,Li, Jianxiao,Zhu, Zhongzhi,Jiang, Huanfeng
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p. 3424 - 3432
(2019/04/01)
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- Transformation of Alkynes into α- Or β-Difluorinated Alkyl Azides by an Efficient One-Pot Two-Step Procedure
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Reported herein an unprecedented 1,2-azide migratory hydroazidation and subsequent gem-difluorination of alkynes accessing β-difluorinated alkyl azides. Importantly, functional group controlled 1,2-azide or 1,2-aryl migration was observed in the case of a
- Li, Huaizhi,Prasad Reddy, Bhoomireddy Rajendra,Bi, Xihe
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supporting information
p. 9358 - 9362
(2019/12/02)
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- BF3·OEt2-Catalyzed Vinyl Azide Addition to in Situ Generated N-Acyl Iminium Salts: Synthesis of 3-Oxoisoindoline-1-acetamides
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BF3·OEt2-catalyzed nucleophilic addition of vinyl azides to in situ generated N-acyl iminium salts obtained from 3-hydroxyisoindolinones is described in this article. The procedure is operationally simple, mild, additive, and metal-free. The reaction proceeds smoothly at ambient temperature with a wide range of 3-hydroxyisoindol-1-ones and vinyl azides to afford 3-oxoisoindoline-1-acetamides (32 examples) in high yields (up to 97%). Furthermore, the synthetic utility of this methodology is depicted by exploiting the reactivity of an amide functionality in the products.
- Kumar Das, Deb,Kannaujiya, Vinod Kumar,Sadhu, Milon M.,Ray, Sumit Kumar,Singh, Vinod K.
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p. 15865 - 15876
(2019/12/24)
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- Electrochemical synthesis of enaminones: Via a decarboxylative coupling reaction
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An environmentally benign and efficient electrochemical synthesis of enaminones via a decarboxylative coupling reaction of α-keto acids using n-Bu4NI as a redox catalyst and electrolyte under constant current electrolysis in an undivided cell is reported. A broad vinyl azide substrate scope and high functional group tolerance are observed. A gram-scale reaction further demonstrates the practicability of the protocol. The results of cyclic voltammetry and control experiments indicate that I2 is likely the active species to initiate the oxidative decarboxylation via an acyl hypoiodite intermediate.
- Kong, Xianqiang,Liu, Yulong,Lin, Long,Chen, Qianjin,Xu, Bo
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p. 3796 - 3801
(2019/07/31)
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- Direct Assembly of 4-Substituted Quinolines with Vinyl Azides as a Dual Synthon via C=C and C-N Bond Cleavage
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An unprecedented Zn-promoted selective cleavage of vinyl azides for the synthesis of 4-substituted quinolines is developed. In this conversion, vinyl azides function as a dual synthon via C=C and C-N bond cleavage with two C=C bonds and one C=N bond formation in a one-step manner. The reaction is appreciated for its readily accessible substrates, high step economy, mild conditions, and use of air as the sole oxidant.
- Cen, Jinghe,Li, Jianxiao,Zhang, Yu,Zhu, Zhongzhi,Yang, Shaorong,Jiang, Huanfeng
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supporting information
p. 4434 - 4438
(2018/08/07)
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- Application of 2-aryl substituted pyrrole compound in medicine for killing oncomelania hupensis
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The invention relates to an application of 2-aryl substituted pyrrole compound in a medicine for killing oncomelania hupensis and belongs to the technical field of prevention and treatment of bilharziasis, and particularly provides the chemical structure of the 2-aryl substituted pyrrole compound and a preparation method of same. The 2-aryl substituted pyrrole compound, being an active component,is used for preparing the snail killing agent in the forms of suspending agents, emulsions and micro-emulsions for killing the oncomelania hupensis. Immersion killing use amount of the 2-aryl substituted pyrrole compound being the active component of the snail killing agent is 0.1-10.00 mg/l, and immersion killing time is 24-72 h. The use amount of spray application is 1-10 g/m and action timeis 3-7 days. Experiment proves that the 2-aryl substituted pyrrole compound has killing activity on the oncomelania hupensis and is lower than a snail killing agent, niclosamide, in the prior art in toxicity on aquatic organisms. The compound can be processed to prepare the snail killing agents and applied in the field of prevention and treatment of bilharziasis.
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Paragraph 0072; 0074; 0075; 0077
(2019/01/08)
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- Application of 2-aryl substituted pyrrole compound in medicine for killing biomphalarid snails
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The invention relates to an application of 2-aryl substituted pyrrole compound in a medicine for killing biomphalarid snails and belongs to the technical field of prevention and treatment of bilharziasis, and particularly provides the chemical structure of the 2-aryl substituted pyrrole compound and a preparation method of same. The 2-aryl substituted pyrrole compound, being an active component, is used for preparing the snail killing agent in the forms of suspending agents, emulsions and micro-emulsions for killing the biomphalarid snail. Immersion killing use amount of the 2-aryl substitutedpyrrole compound being the active component of the snail killing agent is 0.5-10.00 mg/l, and immersion killing time is 24-72 h. Experiment proves that the 2-aryl substituted pyrrole compound has killing activity on the biomphalarid snails and is lower than a snail killing agent, niclosamide, in the prior art in toxicity on aquatic organisms. The compound can be processed to prepare the snail killing agents and applied in the field of prevention and treatment of bilharziasis.
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Paragraph 0080; 0082; 0085
(2019/01/08)
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- Rh-Catalyzed Reaction of Vinyl Azides with Isonitriles and Alkynes/Benzynes
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In contrast to well-known transformations of vinyl azides via azirine intermediates or initiating at the alkene moiety, herein we report a Rh(I)-catalyzed coupling reaction of vinyl azides with isonitriles at the azide moiety to form active vinyl carbodiimide intermediates and following tandem cyclization with unsaturated compounds, such as alkynes and benzynes, to give different classes of azaheterocycles. Mechanistically, controlled experiments and DFT calculations disclose that Rh-nitrene is the vital species in the first coupling step, and the Rh(I) catalyst can also play an important role in the cyclization step of alkynes.
- Li, Zongyang,Huo, Tongyu,Li, Li,Feng, Shuo,Wang, Qian,Zhang, Zhen,Pang, Sen,Zhang, Zhiyuan,Wang, Peng,Zhang, Zhenhua
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supporting information
p. 7762 - 7766
(2019/01/04)
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- Synthesis method for preparing a large amount of alpha-vinyl azide compounds
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The invention relates to a synthesis method for preparing a large amount of alpha-vinyl azide compounds, and belongs to the technical field of organic synthesis chemistry. In the prior art, alpha-vinyl azide compounds have unique reactivity, the synthesis and the applications of the alpha-vinyl azide compounds are important, and the alpha-vinyl azide compounds have good application prospects in the field of organic synthesis. According to the present invention, a large amount of stereospecific alpha-vinyl azide compounds are subjected to one-step efficient synthesis by using the simple and easily-available raw material acetylene-based compound and the azidotrimethylsilane; the synthesis method has advantages of simple and easily-available raw materials, wide application, low catalyst consumption, batch synthesis, simple operation method and efficient reaction, and is suitable for synthesis of a large amount of alpha-vinyl azide compounds; and the product has the stereospecific structure.
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Paragraph 0029; 0033; 0035; 0036; 0090
(2018/07/07)
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- A supramolecular photocatalyst composed of a polyoxometalate and a photosensitizing water-soluble porphyrin diacid for the oxidation of organic substrates in water
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A diprotonated form of a cationic water-soluble saddle-distorted porphyrin (H416+) forms stable supramolecular assemblies with multianionic polyoxometalates (POMs) by electrostatic interactions. An assembly of H416+ with a Ru-substituted POM can perform photocatalytic oxidation of organic substrates in water under visible-light irradiation through adduct formation of the H416+ moiety with an oxidant.
- Ishizuka, Tomoya,Ohkawa, Shumpei,Ochiai, Hidemi,Hashimoto, Muneaki,Ohkubo, Kei,Kotani, Hiroaki,Sadakane, Masahiro,Fukuzumi, Shunichi,Kojima, Takahiko
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supporting information
p. 1975 - 1980
(2018/05/23)
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- [1+1+3] Annulation of Diazoenals and Vinyl Azides: Direct Synthesis of Functionalized 1-Pyrrolines through Olefination
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A dirhodium carboxylate catalyzed [1+1+3] annulation reaction of diazoenals and vinyl azides that gives synthetically important enal-functionalized 1-pyrroline derivatives was developed. The reaction involves a novel rhodium-catalyzed olefination of diazoenals with vinyl azides via electrophilic enal carbenoids, resulting in a new class of enal acrylates. The annulation reaction was used for the direct synthesis of valuable deuterated 1-pyrrolines. Structural diversification of the enal-functionalized 1-pyrrolines resulted in the biologically important pyrrolidine-fused oxaziridine, amino acid derivatives, and a 6-azabicyclo[3.2.1]octane motif present in polycyclic alkaloids.
- Kanchupalli, Vinaykumar,Katukojvala, Sreenivas
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p. 5433 - 5437
(2018/04/09)
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- Eosin Y- and Copper-Catalyzed Dark Reaction to Construct Ene-γ-Lactams
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Eosin Y, a common organo-photocatalyst in visible-light photoredox processes, was found to show excellent catalytic activities for thermal redox reactions under a catalytic amount of Cu(OAc)2. With this catalytic system, vinyl azides and ketene silyl acetals combine to form formal [3 + 2] cycloadducts by α-ester radical addition without light irradiation. This method provides a mild and straightforward paradigm to prepare important synthons of five-membered ene-γ-lactams and bridge ring lactams. It is the first example of an eosin Y-catalyzed redox reaction in the dark.
- Lei, Wen-Long,Feng, Kai-Wen,Wang, Tao,Wu, Li-Zhu,Liu, Qiang
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p. 7220 - 7224
(2018/11/25)
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- Lewis Acid Catalyzed Diastereoselective Cycloaddition Reactions of Donor-Acceptor Cyclopropanes and Vinyl Azides: Synthesis of Functionalized Azidocyclopentane and Tetrahydropyridine Derivatives
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Lewis acid catalyzed [3 + 2]-cycloaddition reaction of donor-acceptor cyclopropanes with vinyl azides has been developed to obtain diastereomerically enriched azidocyclopentane derivatives. In addition, thermal chemoselective ring expansion of azidocyclopentanes to tetrahydropyridine derivatives and further diastereospecific reduction to a substituted piperidine derivative, with an excellent yield, was also achieved.
- Dey, Raghunath,Banerjee, Prabal
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supporting information
p. 304 - 307
(2017/04/21)
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- Ligand-Accelerated Gold-Catalyzed Addition of in Situ Generated Hydrazoic Acid to Alkynes under Neat Conditions
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The direct addition of in situ generated hydrazoic acid to alkynes is realized without solvent by using a gold catalyst derived from a recently designed remotely functionalized biaryl-2-ylphosphine ligand (i.e., WangPhos). With terminal alkynes, the addit
- Li, Xiaoqing,Liao, Shengrong,Wang, Zhixun,Zhang, Liming
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supporting information
p. 3687 - 3690
(2017/07/26)
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- Radical Enamination of Vinyl Azides: Direct Synthesis of N-Unprotected Enamines
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An electron-withdrawing-group-generable radical-induced enamination of vinyl azides is reported, which results in a variety of β-functionalized N-unprotected enamines in a stereoselective manner. A plausible mechanism involving an unusual 1,3-H transfer of in situ generated iminyl radical intermediate was proposed on the basis of experimental results and DFT calculations.
- Ning, Yongquan,Zhao, Xue-Feng,Wu, Yan-Bo,Bi, Xihe
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supporting information
p. 6240 - 6243
(2017/11/24)
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- Tf 2 NH-Catalyzed 1,6-Conjugate Addition of Vinyl Azides with p -Quinone Methides: A Mild and Efficient Method for the Synthesis of β-Bis-Arylamides
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Tf 2 NH-catalyzed tandem 1,6-conjugate addition/Schmidt type rearrangement using vinyl azides and p -quinone methides to access a variety of β-bis-arylated amides is reported. The method is quick, efficient, mild, and high yielding with broad substrate scope.
- Rathod, Jayant,Sharma, Brijesh M.,Mali, Pramod S.,Kumar, Pradeep
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supporting information
p. 5224 - 5230
(2017/10/06)
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- Photoredox-catalysed redox-neutral trifluoromethylation of vinyl azides for the synthesis of α-trifluoromethylated ketones
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A redox-neutral, mild, and simple protocol is developed for the synthesis of α-trifluoromethylated ketones from vinyl azides under transition-metal-free conditions. In the presence of organic photoredox catalyst N-methyl-9-mesityl acridinium and sodium trifluoromethanesulfinate, a broad range of substituted vinyl azides were found to react smoothly upon visible-light irradiation, readily furnishing the corresponding products in satisfied yields.
- Qin, Hai-Tao,Wu, Shu-Wei,Liu, Jia-Li,Liu, Feng
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p. 1696 - 1699
(2017/02/10)
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- Iron-Catalyzed Synthesis of 2H-Imidazoles from Oxime Acetates and Vinyl Azides under Redox-Neutral Conditions
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A novel and versatile method for the synthesis of 2H-imidazoles via iron-catalyzed [3 + 2] annulation from readily available oxime acetates with vinyl azides has been developed. This denitrogenative process involved N-O/N-N bond cleavages and two C-N bond formations to furnish 2,4-substituted 2H-imidazoles. This protocol was performed under mild reaction conditions and needed no additives or ligands. Furthermore, this is a green reaction involving oxime acetate as internal oxidant, acetic acid, and nitrogen as byproducts.
- Zhu, Zhongzhi,Tang, Xiaodong,Li, Jianxiao,Li, Xianwei,Wu, Wanqing,Deng, Guohua,Jiang, Huanfeng
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supporting information
p. 1370 - 1373
(2017/03/23)
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- [3+2] Annulation of Donor-Acceptor Cyclopropanes with Vinyl Azides
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A Sc(OTf)3-catalyzed reaction of vinyl azides with donor-acceptor cyclopropanes affords highly functionalized azidocyclopentanes in a diastereoselective fashion. The resulting azidocyclopentanes could be transformed into various cyclic scaffolds.
- Kaga, Atsushi,Gandamana, Dhika Aditya,Tamura, Sayako,Demirelli, Mesut,Chiba, Shunsuke
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p. 1091 - 1095
(2017/05/19)
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- Visible-Light Photoredox Catalyzed Three-Component Cyclization of 2H-Azirines, Alkynyl Bromides, and Molecular Oxygen to Oxazole Skeleton
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A novel three-component cyclization of 2H-azirines, alkynyl bromides, and molecular oxygen under visible-light photoredox catalysis at room temperature has been developed, which provides a direct approach to a wide range of substituted oxazoles in moderate to good yields.
- Chen, Lili,Li, Hongji,Li, Pinhua,Wang, Lei
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p. 3646 - 3649
(2016/08/16)
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- Preparation method of polysubstituted 3-alkynyl pyrrole derivative
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The invention relates to a preparation method of a polysubstituted 3-alkynyl pyrrole derivative, wherein the method includes a step of performing a ring-opening reaction to 2H-azirine, which is prepared through a simple method, with a terminal alkyne to prepare the polysubstituted 3-alkynyl pyrrole derivative. The 2H-azirine can be easily prepared with initial raw materials which are low in cost and easy to obtain, and the reaction of subsequently preparing the 3-alkynyl pyrrole derivative is simple in operation and is mild in conditions.
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- Palladium-Catalyzed C-H Functionalization of Aromatic Oximes: A Strategy for the Synthesis of Isoquinolines
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An efficient strategy for synthesis of isoquinolines via Pd(II)-catalyzed cyclization reaction of oximes with vinyl azides or homocoupling of oximes is reported. Oximes could serve as a directing group and an internal oxidant in the transformation. This reaction features good functional group tolerance and provides a useful protocol for the synthesis of different kinds of isoquinolines under mild conditions. Some control experiments and 15N isotope labeling experiments were conducted for the mechanistic research. (Chemical Equation Presented).
- Zhu, Zhongzhi,Tang, Xiaodong,Li, Xianwei,Wu, Wanqing,Deng, Guohua,Jiang, Huanfeng
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p. 1401 - 1409
(2016/03/01)
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- Synthesis of α-Fluoroketones from Vinyl Azides and Mechanism Interrogation
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An efficient and mild fluorination of vinyl azides for the synthesis of α-fluoroketones is described. The mechanistic studies indicated that a single-electron transfer (SET) and a subsequent fluorine atom transfer process could be involved in the reaction.
- Wu, Shu-Wei,Liu, Feng
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p. 3642 - 3645
(2016/08/16)
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