- Tertiary amines acting as Alkyl radical equivalents enabled by a P/N heteroleptic Cu(I) photosensitizer
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An unprecedented exploration of tertiary amines as alkyl radical equivalents for cross-coupling with aromatic alkynes to access allylarenes has been achieved by a P/N heteroleptic Cu(I)based photosensitizer under photoredox catalysis conditions. Mechanist
- Zheng, Limeng,Jiang, Qinfang,Bao, Hanyang,Zhou, Bingwei,Luo, Shu-Ping,Jin, Hongwei,Wu, Huayue,Liu, Yunkui
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supporting information
p. 8888 - 8893
(2020/11/30)
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- Gold-Catalyzed Cycloisomerization/1,5-H Migration/Diels-Alder Reaction Cascade: Synthesis of Complex Nitrogen-Containing Heterocycles
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An unprecedented gold-catalyzed cycloisomerization/1,5-H migration/Diels-Alder reaction cascade has been developed that enables the rapid construction of complex nitrogen polycyclic compounds. This one-pot, three-step cascade reaction offers good yields o
- Zhang, Shuyao,Cheng, Beiming,Wang, Shen-An,Zhou, Ling,Tung, Chen-Ho,Wang, Jianwu,Xu, Zhenghu
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supporting information
p. 1072 - 1075
(2017/03/15)
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- Synthesis of N-Heteroaromatic Compounds through Cyclocarbonylative Sonogashira Reactions
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A protocol based on cyclocarbonylative Sonogashira reactions has been developed for the synthesis of nitrogen-containing heterocycles. The process is carried out under CO pressure, in the presence of a small amount of PdCl2(PPh3)sub
- Aronica, Laura Antonella,Albano, Gianluigi,Giannotti, Luca,Meucci, Elisa
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supporting information
p. 955 - 963
(2017/02/15)
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- Synthesis of spiroaminals and spiroketals with bimetallic relay catalysis
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A novel tandem metal relay catalytic system was developed by combining gold-catalyzed cycloisomerization with an early transition-metal-catalyzed inverse-electron-demand hetero-Diels-Alder (IED-HDA) reaction. Various biologically important spiroaminals an
- Wang, Xianghua,Dong, Shuli,Yao, Zhili,Feng, Lei,Daka, Philias,Wang, Hong,Xu, Zhenghu
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supporting information
p. 22 - 25
(2014/01/23)
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- Visible-light-induced chemoselective deboronative alkynylation under biomolecule-compatible conditions
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Here, we report a visible-light-induced deboronative alkynylation reaction, which is redox-neutral and works with primary, secondary and tertiary alkyl trifluoroborates or boronic acids to generate aryl, alkyl and silyl substituted alkynes. This reaction is highly chemoselective and performs well on substrates containing alkenes, alkynes, aldehydes, ketones, esters, nitriles, azides, aryl halides, alkyl halides, alcohols, and indoles, with no detectable occurrence of side reactions. The mechanism of this novel C(sp3)-C(sp) bond coupling reaction was investigated by luminescence quenching, radical trapping, on-off light, and 13C-isotopic-labeling experiments. This reaction can be performed in neutral aqueous conditions, and it is compatible with amino acids, nucleosides, oligosaccharides, nucleic acids, proteins, and cell lysates.
- Huang, Hanchu,Zhang, Guojin,Gong, Li,Zhang, Shuaiyan,Chen, Yiyun
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supporting information
p. 2280 - 2283
(2014/03/21)
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- Formation of indoles, dihydroisoquinolines, and dihydroquinolines by ruthenium-catalyzed heterocyclizations
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Indoles, dihydroisoquinolines, and dihydroquinolines were efficiently prepared by ruthenium-catalyzed heterocyclizations of aromatic homo- and bis-homopropargyl amines/amides in the presence of an amine/ammonium base-acid pair. These regioselective 5-endo and 6-endo cyclizations most probably occur by nucleophilic trapping of key ruthenium-vinylidene intermediates. Georg Thieme Verlag Stuttgart · New York.
- Varela-Fernández, Alejandro,Varela, Jesús A.,Saá, Carlos
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p. 3285 - 3295
(2013/01/15)
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- Metal-free oxidative trifluoromethylthiolation of terminal alkynes with CF3SiMe3 and elemental sulfur
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A metal-free oxidative trifluoromethyl-thiolation of terminal alkynes using readily available CF3SiMe3 and elemental sulfur at room temperature has been developed. This reaction provides an efficient and convenient method for the preparation of alkynyl trifluoromethyl sulfides bearing a wide range of functional groups. Preliminary investigation revealed that elemental sulfur instead of air acted as the oxidant.
- Chen, Chao,Chu, Lingling,Qing, Feng-Ling
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supporting information; experimental part
p. 12454 - 12457
(2012/09/05)
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- Ruthenium-catalyzed cycloisomerization of aromatic homo- and bis-homopropargylic amines/amides: Formation of indoles, dihydroisoquinolines and dihydroquinolines
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Ruthenium-catalyzed cycloisomerizations of aromatic homo- and bis-homopropargylic amines/amides efficiently afford indoles, dihydroisoquinolines and dihydroquinolines. These processes were regioselective (5- and 6-endo cyclizations) on using key Ru vinylidene intermediates. The presence of an amine/ammonium base-acid pair increased the rate of cyclization and facilitated the catalytic turnover. Copyright
- Varela-Fernandez, Alejandro,Varela, Jesus A.,Saa, Carlos
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supporting information; experimental part
p. 1933 - 1937
(2011/10/08)
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- Copper-catalyzed cross-coupling of alkyl and aryl grignard reagents with alkynyl halides
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(Chemical Equation Presented) Good old copperl A new general procedure to couple aliphatic and aromatic Grignard reagents with alkynyl halides under copper catalysis is described (see scheme; NMP=N-methylpyrrolidinone). The reaction is chemoselective and allows preparation of a vast array of simple and functionalized internal alkynes in high yields.
- Cahiez, Gerard,Gager, Olivier,Buendia, Julien
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supporting information; experimental part
p. 1278 - 1281
(2010/05/18)
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- Block modification of rod-shaped π conjugated carbon frameworks with donor and acceptor groups toward highly fluorescent molecules: Synthesis and emission characteristics
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To create organic molecules that are highly fluorescent at a longer wavelength region, we investigated the synthesis (using Pd-catalyzed cross-coupling) and photophysical properties (Φ f, λ em, τ , λ abs, and ε ) of the following π conjugated molecular rods consisting of p-phenyleneethynylene units modified by donor (OMe) and/or acceptor (CN) groups: (1) side-donor modification systems (SD systems), (2) side-acceptor modification systems (SA systems), and (3) systems consisting of a donor block and an acceptor block (BL systems). As a consequence, very high Φ f values (>0.95) were obtained for BL systems. Bathochromic shifts of λ em for the same π conjugation length were largest for BL systems. Thus we succeeded in creating highly efficient light emitters at a longer wavelength region by block modification (e.g., Φ f = 0.97, λ em = 464 nm for BL-9). Considerably intense solid emission (Φ f ~ 0.5) at a longer wavelength region (500- 560 nm) was also found for BL systems. It has been found that BL-6 and BL-8 exhibit interesting two photon absorption characteristics. This journal is The Royal Society of Chemistry.
- Ochi, Takanori,Yamaguchi, Yoshihiro,Wakamiya, Tateaki,Matsubara, Yoshio,Yoshida, Zen-Ichi
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supporting information; scheme or table
p. 1222 - 1231
(2008/10/09)
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- New fluorophores with rod-shaped polycyano π-conjugated structures: Synthesis and photophysical properties
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Novel rod-shaped polycyano-oligo(phenyleneethynylene)s were synthesized by Pd cross-coupling reaction. Polycyano groups were found to greatly improve the emission efficiency (Φf) of OPEs. By the end donor modification, we achieved the creation of very intense blue light-emitting fluorophore with the SMe group (Φf) = 0.972, log ε 4.89, λ em 455 nm) and very intense yellow light-emitting fluorophore with the NMe2 group (Φf = 0.999, log ε 4.75, λem 555 nm). Contrasting Φf solvent dependency of 6 and 7 and a linear relationship between Φf and σp-X over the whole region of σp-X were also found.
- Yamaguchi, Yoshihiro,Ochi, Takanori,Wakamiya, Tateaki,Matsubara, Yoshio,Yoshida, Zen-Ichi
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p. 717 - 720
(2007/10/03)
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- Pharmaceutical compositions comprising aryl-substituted acyclic enediyne compounds
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A pharmaceutical compositions comprises a compound of formula (I): or a pharmaceutically acceptable salt thereof: wherein R1═R2 ═H; or R1 and R2 together form a moiety represented by the formula R3 re
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Page/Page column 13; 15
(2008/06/13)
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- Synthesis and preliminary testing of molecular wires and devices
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Presented here are several convergent synthetic routes to conjugated oligo(phenylene ethynylene)s. Some of these oligomers are free of functional groups, while others possess donor groups, acceptor groups, porphyrin interiors, and other heterocyclic interiors for various potential transmission and digital device applications. The syntheses of oligo(phenylene ethynylene)s with a variety of end groups for attachment to numerous metal probes and surfaces are presented. Some of the functionalized molecular systems showed linear, wire-like, current versus voltage (I(V)) responses, while others exhibited nonlinear I(V) curves for negative differential resistance (NDR) and molecular random access memory effects. Finally, the syntheses of functionalized oligomers are described that can form self-assembled monolayers on metallic electrodes that reduce the Schottky barriers. Information from the Schottky barrier studies can provide useful insight into molecular alligator clip optimizations for molecuar electronics.
- Tour, James M.,Rawlett, Adam M.,Kozaki, Masatoshi,Yao, Yuxing,Jagessar, Raymond C.,Dirk, Shawn M.,Price, David W.,Reed, Mark A.,Zhou, Chong-Wu,Chen, Jia,Wang, Wenyong,Campbell, Ian
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p. 5118 - 5134
(2007/10/03)
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- Double anionic cycloaromatization of 2-(6-substituted-3-hexene-1,5-diynyl)-benzonitriles initiated by methoxide addition
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Formula presented Treatment of 2-((3Z)-undecene-1,5-diynyl)benzonitrile with 5 equiv of sodium methoxide in refluxing methanol for 16 h gave 1-pentyl-6-methoxyphenanthridine in 12% yield, 1-pentyl-6-phenanthridone in 6% yield, and 2-(2-pentyl-6-methoxyphe
- Wu, Ming-Jung,Lin, Chi-Fong,Chen, Shang-Hung
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p. 767 - 768
(2008/02/12)
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- Attempts at vinyl radical carbonylation through cyclization onto carbonyl and cyano groups
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Sulfanylvinyl radicals 4-6, 16, produced from toluenesulfanyl radical addition to alkynes 1-3, 15, gave only products arising from cyclization onto the thiophenyl ring and H-abstraction. No products were obtained deriving from possible 5-membered cyclization onto the esteric or thioesteric carbonyl group. Similar results were obtained from toluenesulfanyl radical addition to alkynyl nitriles 20 and 24, which did not provided any evidence for 5- or 6-membered vinyl radical cyclization onto the aliphatic cyano group. In contrast, both toluenesulfanyl- and benzenesulfanyl- vinyl radicals 32 and 37a smoothly cyclize onto the aromatic cyano group leading to ketones 35 and 39. This protocol represents a novel indirect radical carbonylation and provides a useful synthetic approach to indenones.
- Montevecchi, Pier Carlo,Navacchia, Maria Luisa,Spagnolo, Piero
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p. 8207 - 8216
(2007/10/03)
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- Association of dicyanodiphenylacetylenes with silver(I) salts in solution and solid state: Electrospray ionization mass spectrometry samples aggregates at subsaturated concentrations
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Complexes of 2,3'-dicyanodiphenylacetylene (2,3'-DCPA, 1), 2,2'-dicyanodiphenylacetylene (2,2'-DCPA, 2), and 2,4'-dicyanodiphenylacetylene (2,4'-DCPA, 3) with silver(I) salts have been characterized in the solid state by single-crystal X-ray analysis. In
- Hirsch, Keith A.,Wilson, Scott R.,Moore, Jeffrey S.
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p. 10401 - 10412
(2007/10/03)
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- Cross-Coupling Reactions of Monosubstituted Acetylenes and Aryl Halides Catalysed by Palladium on Charcoal
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A convenient procedure for the Pd(O) catalyzed cross-coupling of monosubstituted acetylenes with aryl halides, in which palladium on charcoal serves as the source of the noble metal, is described.
- Rosa, Martha A. De la,Velarde, Esperanza,Guzman, Angel
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p. 2059 - 2064
(2007/10/02)
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- Condensed Heteroaromatic Ring Systems. III. Synthesis of Naphthyridine Derivatives by Cyclization of Ethynylpyridinecarboxamides
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Four kinds of naphthyridinones, i.e. 1,6-naphthyridin-5-one, 1,7-naphthyridin-8-one, 2,6-naphthyridin-2-one, and 2,7-naphthyridin-1-one derivatives, were commonly synthesized by the intramolecular cyclization of pyridinecarboxamides having an ethynyl group or β,β-dimethoxyethyl group adjacent to the carbamoyl group.The syntheses of the starting pyridine derivatives were easily accomplished by cross-coupling of the corresponding halopyridines with acetylenes.Keywords-intramolecular cyclization; palladium catalyst; trimethylsilylacetylene; naphthyridinone; pyridineacetaldehyde; 1(2H)-isoquinolone
- Sakamoto, Takao,Kondo, Yoshinori,Yamanaka, Hiroshi
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p. 626 - 633
(2007/10/02)
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