- Design of an Electron-Withdrawing Benzonitrile Ligand for Ni-Catalyzed Cross-Coupling Involving Tertiary Nucleophiles
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The design of new ligands for cross-coupling is essential for developing new catalytic reactions that access valuable products such as pharmaceuticals. In this report, we exploit the reactivity of nitrile-containing additives in Ni catalysis to design a benzonitrile-containing ligand for cross-coupling involving tertiary nucleophiles. Kinetic and Hammett studies are used to elucidate the role of the optimized ligand, which demonstrate that the benzonitrile moiety acts as an electron-acceptor to promote reductive elimination over β-hydride elimination and stabilize low-valent Ni. With these conditions, a protocol for decyanation-metalation and Ni-catalyzed arylation is conducted, enabling access to quaternary α-arylnitriles from disubstituted malononitriles.
- Edjoc, Racquel K.,Mills, L. Reginald,Rousseaux, Sophie A. L.
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p. 10422 - 10428
(2021/07/26)
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- Palladium-Catalyzed Direct α-Arylation of Arylacetonitriles with Aryl Tosylates and Mesylates
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The first general palladium-catalyzed α-arylation of arylacetonitriles with aryl and heteroaryl sulfonates are reported. Pd(OAc)2 associated with XPhos serves as the effective catalyst to facilitate this reaction. A broad range of electron-rich, -neutral, -deficient, and sterically hindered aryl/heteroaryl tosylates and mesylates are coupled with arylacetonitriles bearing different substituents to give the corresponding products in good to excellent yields. Catalyst loading down to 0.1 mol-% Pd was achieved, and 22 unprecedented compounds were synthesized from 43 demonstrated examples using this method. Its applicability with the modification of biological phenolic compounds was successfully demonstrated. The Pd/XPhos system catalyzed the α-arylation and followed by alkylation in one-pot sequential conditions, resulting in the direct synthesis of compounds containing quaternary center- and deuterium-containing compounds in good to excellent yields.
- Yuen, On Ying,Chen, Xiangmeng,Wu, Junyu,So, Chau Ming
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p. 1912 - 1916
(2020/03/13)
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- SUMO INHIBITOR COMPOUNDS AND USES THEREOF
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The present invention relates to compounds and compositions capable of acting as inhibitors of small ubiquitin-like modifier (SUMO) family of proteins. The compounds and compositions may be used in the treatment of cancer. There are disclosed, inter alia, methods of inhibiting an E1 enzyme, and compounds useful for inhibiting an E1 enzyme.
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Paragraph 0204
(2020/10/09)
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- Synthesis of Nitrile-Bearing Quaternary Centers by an Equilibrium-Driven Transnitrilation and Anion-Relay Strategy
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The efficient preparation of nitrile-containing building blocks is of interest due to their utility as synthetic intermediates and their prevalence in pharmaceuticals. As a result, significant efforts have been made to develop methods to access these motifs which rely on safer and non-toxic sources of CN. Herein, we report that 2-methyl-2-phenylpropanenitrile is an efficient, non-toxic, electrophilic CN source for the synthesis of nitrile-bearing quaternary centers by a thermodynamic transnitrilation and anion-relay strategy. This one-pot process leads to nitrile products resulting from the gem-difunctionalization of alkyl lithium reagents.
- Alazet, Sébastien,West, Michael S.,Patel, Purvish,Rousseaux, Sophie A. L.
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supporting information
p. 10300 - 10304
(2019/07/04)
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- Transfer Hydrocyanation of α- and α,β-Substituted Styrenes Catalyzed by Boron Lewis Acids
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A straightforward gram-scale preparation of cyclohexa-1,4-diene-based hydrogen cyanide (HCN) surrogates is reported. These are bench-stable but formally release HCN and rearomatize when treated with Lewis acids. For BCl3, the formation of the isocyanide adduct [(CN)BCl3]? and the corresponding Wheland complex was verified by mass spectrometry. In the presence of 1,1-di- and trisubstituted alkenes, transfer of HCN from the surrogate to the C?C double bond occurs, affording highly substituted nitriles with Markovnikov selectivity. The success of this transfer hydrocyanation depends on the Lewis acid employed; catalytic amounts of BCl3 and (C6F5)2BCl are shown to be effective while B(C6F5)3 and BF3?OEt2 are not.
- Orecchia, Patrizio,Yuan, Weiming,Oestreich, Martin
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supporting information
p. 3579 - 3583
(2019/02/05)
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- Hydride Reduction by a Sodium Hydride-Iodide Composite
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Sodium hydride (NaH) is widely used as a Br?nsted base in chemical synthesis and reacts with various Br?nsted acids, whereas it rarely behaves as a reducing reagent through delivery of the hydride to polar π electrophiles. This study presents a series of reduction reactions of nitriles, amides, and imines as enabled by NaH in the presence of LiI or NaI. This remarkably simple protocol endows NaH with unprecedented and unique hydride-donor chemical reactivity.
- Too, Pei Chui,Chan, Guo Hao,Tnay, Ya Lin,Hirao, Hajime,Chiba, Shunsuke
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supporting information
p. 3719 - 3723
(2016/03/26)
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- Synthesis of indolines by copper-mediated intramolecular aromatic C-H amination
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A Cu(OAc)2-mediated intramolecular aromatic C-H amination proceeds with the aid of a picolinamide-type bidentate coordination group to deliver the corresponding indolines in good yields. The reaction occurs smoothly even under noble-metal-free conditions, and in some cases the use of an MnO2 terminal oxidant renders the process catalytic in Cu. The mild oxidation aptitude of Cu(OAc)2 and/or MnO2 accommodates the formation of electron-rich thiophene-and indole-fused indoline analogues. The Cu-based system can provide an effective approach to various indolines of potent interest in pharmaceutical and medicinal chemistry.
- Takamatsu, Kazutaka,Hirano, Koji,Satoh, Tetsuya,Miura, Masahiro
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p. 3242 - 3249
(2015/03/30)
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- Fe-catalyzed regiodivergent [1,2]-shift of α-aryl aldehydes
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An Fe-catalyzed conversion of aldehydes to ketones via [1,2]-shift has been developed. This skeletal rearrangement shows a wide substrate scope and chemoselectivity profile while exhibiting an excellent [1,2]-aryl or [1,2]-alkyl shift selectivity that is easily switched by electronic effects.
- Gutierrez-Bonet, Alvaro,Flores-Gaspar, Areli,Martin, Ruben
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supporting information
p. 12576 - 12579
(2013/09/23)
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- β-Amination of saturated nitriles through palladium-catalyzed dehydrogenation, 1,4-addition, and re-dehydrogenation
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Amination at the β-position of 2-arylpropionitriles through catalytic dehydrogenation occurred by using [PdCl2(PMe3) 2] catalyst and bromobenzene. This is the first catalytic reaction involving the direct dehydrogenation of saturated nitriles.
- Ueno, Satoshi,Maeda, Ryohei,Yasuoka, Shohei,Kuwano, Ryoichi
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supporting information
p. 40 - 42
(2013/02/25)
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- Oxidative nucleophilic substitution of hydrogen in nitroarenes with phenylacetonitrile derivatives
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Tertiary carbanions generated from α-substituted phenylacetonitriles in liquid ammonia add to nitrobenzenes in the para position to form the corresponding σ(H)-adducts which are transformed, depending on the starting nitriles and the reaction conditions, to products of oxidative nucleophilic substitution of hydrogen, ONSH or vicarious nucleophilic substitution, VNS.
- Makosza, Mieczyslaw,Stalinski, Krzysztof
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p. 8797 - 8810
(2007/10/03)
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- Nucleophilic Substitution Reactions of Alkyl Halides By Using New Polymer-Supported Reagents Containing Hemin
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A new polymer reagent consisting of hemin, divinylbenzene, and 2-methyl-5-vinylpyridine was synthesized by suspension copolymerization.Substitution reactions of primary, secondary, and tertiary alkyl halides with the hemin copolymer combined with cyanide, azide, and thiocyanate ions were given satisfactory yields.This reaction mechanism was revealed to be a SNi type on the basis of stereochemical study.The hemin copolymer was not only a polymer-supported reagent with functional capabilities, but also served to separate the product from the reaction mixture.
- Saito, Kiyoshi,Harada, Kaoru
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p. 2562 - 2566
(2007/10/02)
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- Molecular Modification of Anticholinergics as Probes for Muscarinic Receptors. Amino Esters of α-Substituted Phenylacetic Acid and Related Analogues
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Two series of compounds having the general structure of C6H5CRR'COOCH2CH2NEt2 were synthesized and examined for their antispasmodic activities.These compounds were selected as structural probes for exploring the nature of muscarinic cholinergic receptor binding sites that interact with atropine-like anticholinergics.These studies indicate a rather strict size limitation for the hydrophobic region of the receptor and suggest intramolecular hydrogen bonding as a possible means to explain the observed stereoselectivity.
- Lu, Mattias C.,Wung, Walley E.,Shih, Lisa B.,Callejas, Soledad,Gearien, James E.,Thompson, Emmanuel B.
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p. 273 - 278
(2007/10/02)
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