A metal-free desulfurizing radical reductive C–C coupling of thiols and alkenes

2019 ◽  
Vol 55 (71) ◽  
pp. 10583-10586 ◽  
Author(s):  
Qixue Qin ◽  
Weijing Wang ◽  
Cheng Zhang ◽  
Song Song ◽  
Ning Jiao
Keyword(s):  
Alkyl Radicals ◽  
Metal Free

An intermolecular reductive C–C coupling of electrophilic alkyl radicals and alkenes has been developed.

scholarly journals Organic photoredox catalysis for the oxidation of silicates: applications in radical synthesis and dual catalysis

2016 ◽  
Vol 52 (64) ◽  
pp. 9877-9880 ◽  
Author(s):  
Christophe Lévêque ◽  
Ludwig Chenneberg ◽  
Vincent Corcé ◽  
Cyril Ollivier ◽  
Louis Fensterbank
Keyword(s):  
Organic Dye ◽  
Photoredox Catalysis ◽  
Alkyl Radicals ◽  
Metal Free ◽  
Dual Catalysis

Metal free photooxidation of alkyl bis(catecholato)silicates with the organic dye 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyano-benzene (4CzIPN) allows the smooth formation of alkyl radicals.

Cross-dehydrogenative coupling of α-C(sp3)–H of ethers/alkanes with C(sp2)–H of heteroarenes under metal-free conditions

2015 ◽  
Vol 13 (46) ◽  
pp. 11341-11350 ◽  
Author(s):  
Srinivas Ambala ◽  
Thanusha Thatikonda ◽  
Shweta Sharma ◽  
Gurunadham Munagala ◽  
Kushalava Reddy Yempalla ◽  
...  
Keyword(s):  
Coupling Method ◽  
Alkyl Radicals ◽  
Metal Free ◽  
Dehydrogenative Coupling

A metal-free cross-dehydrogenative coupling method between α-oxyalkyl/alkyl radicals and electron deficient heteroarenes is reported.

The Shadow Widths of Very Small Particles are Formed Independently of the Metal Cap Build Up on the Particle

1981 ◽  
Vol 39 ◽  
pp. 568-569
Author(s):  
George C. Ruben
Keyword(s):  
Gold Particle ◽  
Film Surface ◽  
Small Particles ◽  
Geometric Process ◽  
Metal Free ◽  
Shadow Area

The formation of shadows behind small particles has been thought to be a geometric process (GP) where the metal cap build up on the particle creates a shadow width the same size as or larger than the particle. This GP cannot explain why gold particle shadow widths are generally larger than the gold particle and may have no appreciable metal cap build up (fig. 1). Ruben and Telford have suggested that particle shadow widths are formed by the width dependent deflection of shadow metal (SM) lateral to and infront of the particle. The trajectory of the deflected SM is determined by the incoming shadow angle (45°). Since there can be up to 1.4 times (at 45°) more SM directly striking the particle than the film surface, a ridge of metal nuclei lateral to and infront of the particle can be formed. This ridge in turn can prevent some SM from directly landing in the metal free shadow area. However, the SM that does land in the shadow area (not blocked by the particle or its ridge) does not stick and apparently surface migrates into the SM film behind the particle.

Recent advancement in the electrocatalytic synthesis of ammonia

Nanoscale ◽  
2020 ◽  
Vol 12 (15) ◽  
pp. 8065-8094 ◽  
Author(s):  
Xudong Wen ◽  
Jingqi Guan
Keyword(s):  
Metal Oxide ◽  
Oxide Catalysts ◽  
Single Atom ◽  
Metal Oxide Catalysts ◽  
Metal Free ◽  
Recent Advancement ◽  
Nanocomposite Catalysts

Different kinds of electrocatalysts used in NRR electrocatalysis (including single atom catalysts, metal oxide catalysts, nanocomposite catalysts, and metal free catalysts) are introduced.

Transition-metal-free catalytic hydroboration reduction of amides to amines

2020 ◽  
Vol 7 (21) ◽  
pp. 3515-3520
Author(s):  
Wubing Yao ◽  
Jiali Wang ◽  
Aiguo Zhong ◽  
Shiliang Wang ◽  
Yinlin Shao
Keyword(s):  
Transition Metal ◽  
Selective Catalytic Reduction ◽  
Catalytic Reduction ◽  
Value Added ◽  
Metal Free

The selective catalytic reduction of amides to value-added amine products is a desirable but challenging transformation.

Deaminative carbonylative thioesterification of activated alkylamines with thiophenols under transition-metal-free conditions

2021 ◽  
Author(s):  
Fengqian Zhao ◽  
Xiao-Feng Wu
Keyword(s):  
Free Radical ◽  
Transition Metal ◽  
Metal Free

A transition-metal-free radical carbonylation of activated alkylamines with thiophenols has been successfully developed. Various thioesters were selectively produced with moderate to good yields.

Stereodivergent Alkyne Hydrofluorination Using a Simple Practical Reagent

2020 ◽  
Author(s):  
Rui Guo ◽  
Xiaotian Qi ◽  
Hengye Xiang ◽  
Paul Geaneoates ◽  
Ruihan Wang ◽  
...  
Keyword(s):  
Bond Formation ◽  
Biologically Active ◽  
Dft Studies ◽  
Thermodynamic Control ◽  
Important Goal ◽  
Peptide Bonds ◽  
Metal Free ◽  
Vinyl Cation ◽  
E And Z Isomers ◽  
Vinyl Fluorides

Vinyl fluorides play an important role in drug development as they serve as bioisosteres for peptide bonds and are found in a range of biologically active molecules. The discovery of safe, general and practical procedures to prepare vinyl fluorides remains an important goal and challenge for synthetic chemistry. Here we introduce an inexpensive and easily-handled reagent and report simple, scalable, and metal-free protocols for the regioselective and stereodivergent hydrofluorination of alkynes to access both the E and Z isomers of vinyl fluorides. These conditions were suitable for a diverse collection of alkynes, including several highly-functionalized pharmaceutical derivatives. Mechanistic and DFT studies support C–F bond formation through a vinyl cation intermediate, with the (E)- and (Z)-hydrofluorination products forming under kinetic and thermodynamic control, respectively.<br>

Copper Catalyzed sp3 C-H α-Acetylation

2019 ◽  
Author(s):  
Otome Okoromoba ◽  
Eun Sil Jang ◽  
Claire McMullin ◽  
Thomas Cundari ◽  
Timothy H. Warren
Keyword(s):  
Natural Products ◽  
Dft Studies ◽  
Alkyl Radicals ◽  
Important Chemical ◽  
Alkyl Electrophiles ◽  
Synthetic Intermediates ◽  
Alkylation Reactions

<p>α-substituted ketones are important chemical targets as synthetic intermediates as well as functionalities in in natural products and pharmaceuticals. We report the sp<sup>3</sup> C-H α-acetylation of sp<sup>3</sup> C-H substrates R-H with arylmethyl ketones ArC(O)Me to provide α-alkylated ketones ArC(O)CH<sub>2</sub>R at RT with <sup>t</sup>BuOO<sup>t</sup>Bu as oxidant via copper(I) β-diketiminato catalysts. Proceeding via alkyl radicals R•, this method enables α-substitution with bulky substituents without competing elimination that occurs in more traditional alkylation reactions between enolates and alkyl electrophiles. DFT studies suggest the intermediacy of copper(II) enolates [Cu<sup>II</sup>](CH<sub>2</sub>C(O)Ar) that capture alkyl radicals R• to give R-CH<sub>2</sub>C(O)Ar under competing dimerization of the copper(II) enolate to give the 1,4-diketone ArC(O)CH<sub>2</sub>CH<sub>2</sub>C(O)Ar.</p>

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