- Correlation between HOMO alignment and contact resistance in molecular junctions: Aromatic thiols versus aromatic isocyanides
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Understanding electron transport in metal-molecule-metal (MMM) junctions is of great importance for the advancement of molecular electronics. Critical factors that determine conductivity in a MMM junction include the nature of metal-molecule contacts and
- Kim, Bongsoo,Beebe, Jeremy M.,Jun, Yongseok,Zhu,Frisbie, G. Daniel
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Read Online
- Metabolic Fate of the Isocyanide Moiety: Are Isocyanides Pharmacophore Groups Neglected by Medicinal Chemists?
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Despite the isolation of hundreds of bioactive isocyanides from terrestrial fungi and bacteria as well as marine organisms, the isocyanide functionality has so far received little attention from a medicinal chemistry standpoint. The widespread tenet that isocyanides are chemically and metabolically unstable has restricted bioactivity studies to their antifouling properties and technical applications. In order to confirm or refute this idea, the hepatic metabolism of six model isocyanides was investigated. Aromatic and primary isocyanides turned out to be unstable and metabolically labile, but secondary and tertiary isocyanides resisted metabolization, showing, in some cases, cytochrome P450 inhibitory properties. The potential therefore exists for the secondary and tertiary isocyanides to qualify them as pharmacophore groups, in particular as war-heads for metalloenzyme inhibition because of their potent metal-coordinating properties.
- Aprile, Silvio,Galli, Ubaldina,Grosa, Giorgio,Tron, Gian Cesare,Purghè, Beatrice
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Read Online
- Enantioselective Synthesis of Azetidines through [3 + 1]-Cycloaddition of Donor-Acceptor Aziridines with Isocyanides
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The enantioselective [3 + 1]-cycloaddition of racemic donor-acceptor (D-A) aziridines with isocyanides was first realized under mild reaction conditions using a chiral N,N′-dioxide/MgIIcomplex as catalyst, providing a facile route to enantioenriched exo-imido azetidines with good to excellent yield (up to 99%) and enantioselectivity (up to 94% ee). An obvious chiral amplification effect was observed in this system, and an explanation was elucidated based on the experimental investigation and X-ray crystal structure of the enantiomerically pure catalyst.
- Zhang, Fengcai,Sang, Xinpeng,Zhou, Yuqiao,Cao, Weidi,Feng, Xiaoming
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supporting information
p. 1513 - 1517
(2022/03/01)
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- Silver-Catalyzed Selective Multicomponent Coupling Reactions of Arynes with Nitriles and Isonitriles
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Pathway selective aryne-based novel multicomponent coupling reactions with isonitriles and nitriles are described. Crucial to these reactions is the formation of a silver-aryne complex, which shows differential reactivity toward isonitriles and nitriles to form two different forms of ortho-nitrilium organosilver arene species. Interception of the nitrilium of an aryne-isonitrile adduct with another isonitrile leads to the formation of benzocyclobutene-1,2-diimines, whereas the nitrilium of an aryne-nitrile adduct renders selective formation of 3H-indol-3-imines or 3-iminoindolin-2-ol depending on the structure of the nitrile employed.
- Ghorai, Sourav,Lin, Yongjia,Xia, Yuanzhi,Wink, Donald J.,Lee, Daesung
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p. 642 - 647
(2020/01/31)
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- Organophosphine-free copper-catalyzed isothiocyanation of amines with sodium bromodifluoroacetate and sulfur
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A copper-catalyzed isothiocyanation of amines with sodium bromodifluoroacetate and sulfur in the absence of organophosphine has been established. This approach represents a simple and efficient one-pot synthesis of isothiocyanates, and features excellent functional group tolerance and the use of a cheap, safe and odorless sulfur source. Moreover, this process could directly provide isothiocyanate analogous bioactive molecules, thiocarbonyl-containing pesticides and facile construction of benzoxazole and benzimidazole frames.
- Feng, Wei,Zhang, Xing-Guo
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supporting information
p. 1144 - 1147
(2019/01/28)
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- [Ph3C][B(C6F5)4]: A Highly Efficient Metal-Free Single-Component Initiator for the Helical-Sense-Selective Cationic Copolymerization of Chiral Aryl Isocyanides and Achiral Aryl Isocyanides
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Commercially available [Ph3C][B(C6F5)4] served as a highly efficient metal-free and single-component initiator not only for the carbocationic polymerization of polar and bulky aryl isocyanides with extremely high activity up to 1.2×107 g of polymer/(molcat. h), but also for the helical-sense-selective polymerization of chiral aryl isocyanides and copolymerization with achiral aryl isocyanides to afford high-molecular-weight functional poly(aryl isocyanide)s with good solubility as well as AIE characteristics and/or a single-handed helical conformation.
- Yan, Xinwen,Zhang, Shaowen,Zhang, Pengfei,Wu, Xiaolu,Liu, An,Guo, Ge,Dong, Yuping,Li, Xiaofang
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p. 8947 - 8952
(2018/07/25)
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- Silver-Catalyzed Chemoselective [4+2] Annulation of Two Isocyanides: A General Route to Pyridone-Fused Carbo- and Heterocycles
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A silver-catalyzed chemoselective [4+2] annulation of aryl and heteroaryl isocyanides with α-substituted isocyanoacetamides was developed for the facile and efficient synthesis of 2-aminoquinolones, naphthyridines, and phenanthrolines. A mechanism for this multistep domino reaction is proposed on the basis of a13C-labeling experiment, according to which an unprecedented chemoselective heterodimerization of two different isocyanides generates an α-amidoketenimine intermediate, which undergoes 1,3-amino migration to form an α-imidoylketene, followed by 6 π electrocyclization.
- Hu, Zhongyan,Dong, Jinhuan,Men, Yang,Lin, Zhichen,Cai, Jinxiong,Xu, Xianxiu
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supporting information
p. 1805 - 1809
(2017/02/05)
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- Discovery of New Selenoureido Analogues of 4-(4-Fluorophenylureido)benzenesulfonamide as Carbonic Anhydrase Inhibitors
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A series of benzenesulfonamides bearing selenourea moieties was obtained considering the ureido-sulfonamide SLC-0111, in Phase I clinical trials as antitumor agent, as a lead molecule. All compounds showed interesting inhibition potencies against the physiologically relevant human (h) carbonic anhydrase (hCAs, EC 4.2.1.1) isoforms I, II, IV, and IX. The most flexible analogues in the series 14-19 showed low nanomolar inhibition constants against hCA I, II, and IX. We assessed selected compounds on the in vitro antioxidant properties and binding modes and evaluated ex vivo human prostate (PC3), breast (MDA-MB-231), and colon-rectal (HT-29) cancer cell lines both in normoxic and hypoxic conditions.
- Angeli, Andrea,Tanini, Damiano,Peat, Thomas S.,Di Cesare Mannelli, Lorenzo,Bartolucci, Gianluca,Capperucci, Antonella,Ghelardini, Carla,Supuran, Claudiu T.,Carta, Fabrizio
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supporting information
p. 963 - 968
(2017/09/22)
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- Synthesis of isocyanides through dehydration of formamides using XtalFluor-E
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The formation of isocyanides from formamides using XtalFluor-E, [Et2NSF2]BF4, is presented. A wide range of formamides can be used to produce the corresponding isocyanides in up to 99% yield. In a number of cases, the crude products showed good purity (generally >80% by NMR) allowing to be used directly in multi-component reactions.
- Keita, Massaba,Vandamme, Mathilde,Mahé, Olivier,Paquin, Jean-Fran?ois
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supporting information
p. 461 - 464
(2015/03/05)
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- Efficient one-pot synthesis of unsymmetrical gold(I) N-heterocyclic carbene complexes and their use as catalysts
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Eleven different gold(I) complexes of new NHC ligands were prepared in excellent yield, demonstrating the versatility of the new route to NHC complexes. While the influence of electronically different ligands on the synthesis of the catalysts was small, the catalytic activities of the products differed significantly.
- Hashmi, A. Stephen K.,Yu, Yang,Rominger, Frank
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experimental part
p. 895 - 904
(2012/04/04)
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- Synthesis and evaluation of inhibitors of bacterial drug efflux pumps of the major facilitator superfamily
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Inhibitors of drug efflux pumps have great potential as pharmacological agents that restore the drug susceptibility of multidrug resistant bacterial pathogens. Most attention has been focused on the discovery of small molecules that inhibit the resistance nodulation division (RND) family drug efflux pumps in Gram-negative bacteria. The prototypical inhibitor of RND-family efflux pumps in Gram-negative bacteria is MC-207,110 (Phe-Arg-β-naphthylamide), a C-capped dipeptide. Here, we report that C-capped dipeptides inhibit two chloramphenicol-specific efflux pumps in Streptomyces coelicolor, a Gram-positive bacterium that is a relative of the human pathogen Mycobacterium tuberculosis. Diversity-oriented synthesis of a library of structurally related C-capped dipeptides via an Ugi four component reaction and screening of the resulting compounds resulted in the discovery of a compound that is threefold more potent as a suppressor of chloramphenicol resistance in S. coelicolor than MC-207,110. Since chloramphenicol resistance in S. coelicolor is mediated by major facilitator superfamily drug efflux pumps, our findings provide the first evidence that C-capped dipeptides can inhibit drug efflux pumps outside of the RND superfamily.
- Okandeji, Babajide O.,Greenwald, Daniel M.,Wroten, Jessica,Sello, Jason K.
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experimental part
p. 7679 - 7689
(2012/02/05)
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- Syntheses of spirocyclic oxindole-butenolides by using three-component cycloadditions of isocyanides, allenoates, and isatins
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Spiro workflow! Efficient syntheses of spirocyclic oxindole-butenolides from readily available isocyanides, allenoates, and isatins are disclosed (see scheme; R1=alkyl, aryl; R2=halide, nitro, methoxy; PG=protecting group). This protocol also allows the insertion of carbon monoxide into organic molecules without the aid of a transition-metal catalyst after the hydrolysis process. Copyright
- Li, Jian,Liu, Yuejin,Li, Chunju,Jia, Xueshun
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p. 7409 - 7413
(2011/08/05)
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