Fe-Catalyzed decarbonylative alkylation–peroxidation of alkenes with aliphatic aldehydes and hydroperoxide under mild conditions

2019 ◽  
Vol 21 (2) ◽  
pp. 269-274 ◽  
Author(s):  
Chuan-Shuo Wu ◽  
Rong Li ◽  
Qi-Qiang Wang ◽  
Luo Yang
Keyword(s):  
Low Temperature ◽  
Aliphatic Aldehydes ◽  
Alkyl Radicals ◽  
Radical Coupling ◽  
Mild Conditions

Decarbonylation at 60–80 °C! Readily available linear/branched aliphatic aldehydes were decarbonylated into 1°, 2° and 3° alkyl radicals at low temperature for cascade radical insertion and radical–radical coupling to construct C(sp3)–C(sp3) and C(sp3)–O bonds.

Pt-Pd Nanoalloy for the Unprecedented Activation of Carbon-Fluorine Bond at Low Temperature

2019 ◽  
Author(s):  
Raghu Nath Dhital ◽  
keigo nomura ◽  
Yoshinori Sato ◽  
Setsiri Haesuwannakij ◽  
Masahiro Ehara ◽  
...  
Keyword(s):  
Activation Energy ◽  
Low Temperature ◽  
Dft Calculations ◽  
Bond Activation ◽  
Mild Conditions ◽  
Selective Transformation ◽  
Rate Determining Step ◽  
Highly Active ◽  
Harsh Conditions ◽  
Reaction Profile

Carbon-Fluorine (C-F) bonds are considered the most inert organic functionality and their selective transformation under mild conditions remains challenging. Herein, we report a highly active Pt-Pd nanoalloy as a robust catalyst for the transformation of C-F bonds into C-H bonds at low temperature, a reaction that often required harsh conditions. The alloying of Pt with Pd is crucial to activate C-F bond. The reaction profile kinetics revealed that the major source of hydrogen in the defluorinated product is the alcoholic proton of 2-propanol, and the rate-determining step is the reduction of the metal upon transfer of the <i>beta</i>-H from 2-propanol. DFT calculations elucidated that the key step is the selective oxidative addition of the O-H bond of 2-propanol to a Pd center prior to C-F bond activation at a Pt site, which crucially reduces the activation energy of the C-F bond. Therefore, both Pt and Pd work independently but synergistically to promote the overall reaction

Enantioselective Radical Functionalization of Imines and Iminium Intermediates via Visible Light Photoredox Catalysis

Synthesis ◽  
2020 ◽  
Author(s):  
Jia-Jia Zhao ◽  
Hong-Hao Zhang ◽  
Shouyun Yu
Keyword(s):  
Visible Light ◽  
Asymmetric Synthesis ◽  
Carbonyl Compounds ◽  
Asymmetric Reduction ◽  
Chemical Transformations ◽  
Photoredox Catalysis ◽  
Radical Coupling ◽  
Mild Conditions ◽  
Iminium Ions ◽  
Radical Functionalization

Visible light photoredox catalysis has recently emerged as a powerful tool for the development of new and valuable chemical transformations under mild conditions. Visible-light promoted enantioselective radical transformations of imines and iminium intermediates provide new opportunities for the asymmetric synthesis of amines and asymmetric β-functionalization of unsaturated carbonyl compounds. In this review, the advance in the catalytic asymmetric radical functionalization of imines, as well as iminium intermediates, are summarized. 1 Introduction 2 The enantioselective radical functionalization of imines 2.1 Asymmetric reduction 2.2 Asymmetric cyclization 2.3 Asymmetric addition 2.4 Asymmetric radical coupling 3 The enantioselective radical functionalization of iminium ions 3.1 Asymmetric radical alkylation 3.2 Asymmetric radical acylation 4 Conclusion

Radical Addition of Hydroxy Quinazolines and Alkylation of Quinones via the Electro-induced Homolysis of 4-Alkyl-1,4-dihydropyridines

Synthesis ◽  
2022 ◽  
Author(s):  
Xiaosheng Luo ◽  
Qiping Feng ◽  
Ping Wang
Keyword(s):  
Radical Addition ◽  
Alkyl Radicals ◽  
Mild Conditions

Herein, we report the formation of C(sp3)-centered radicals via the electro-induced homolysis of 4-alkyl-1,4-dihydropyridines (alkyl-DHPs). The resulting alkyl radicals reacted with hydroxy quinazolines or quinones to afford 2-alkyl dihydroquinazolinones or alkylated quinones. A broad range of alkyl DHPs could be used as versatile radical precursors under electrolysis conditions. This alterative strategy provided a simple and effective pathway for the construction of C(sp2)–C(sp3) and C(sp3)–C(sp3) bonds under mild conditions.

Electrochemical nitrogen reduction to ammonia under mild conditions enabled by a polymer gel electrolyte

2018 ◽  
Vol 54 (34) ◽  
pp. 4250-4253 ◽  
Author(s):  
Benjamin L. Sheets ◽  
Gerardine G. Botte
Keyword(s):  
Low Temperature ◽  
Electrochemical Reduction ◽  
Gel Electrolyte ◽  
Polymer Gel ◽  
Polymer Gel Electrolyte ◽  
Nitrogen Reduction ◽  
Mild Conditions ◽  
Temperature And Pressure

A polymer gel electrolyte was implemented to enable the electrochemical reduction of nitrogen to ammonia at low temperature and pressure.

scholarly journals Low Temperature Chemoselective Hydrogenation of Aldehydes over a Magnetic Pd Catalyst

2019 ◽  
Vol 9 (9) ◽  
pp. 1792
Author(s):  
Liu ◽  
Wang ◽  
Gao ◽  
Wang ◽  
Cheng ◽  
...  
Keyword(s):  
Low Temperature ◽  
Room Temperature ◽  
Heterogeneous Catalysts ◽  
Aromatic Aldehydes ◽  
Pd Catalyst ◽  
Primary Alcohols ◽  
Mild Conditions ◽  
Excellent Yield ◽  
Chemoselective Hydrogenation ◽  
Supported Palladium

Chemoselective hydrogenation of aldehydes with heterogeneous catalysts under mild conditions is of great importance but remains a major challenge. Herein, an efficient strategy was developed for low temperature chemoselective hydrogenation of aldehydes with broad substrate scope over a magnetic material supported palladium catalyst (γ-Fe2O3@HAP-Pd). Aldehydes bearing various reducible functional groups readily underwent hydrogenation to give the corresponding primary alcohols with moderate to excellent yield at room temperature in aqueous solutions. The Hammett equation revealed that the hydrogenation of aromatic aldehydes proceeded via an anionic intermediate. Additionally, when the temperature increased to 70 °C, toluene was obtained by the deoxygenation of benzaldehyde in excellent yield. Furthermore, the γ-Fe2O3@HAP-Pd could be recycled up to six times without loss of activity and metal leaching.

Co-Catalyzed decarbonylative alkylative esterification of styrenes with aliphatic aldehydes and hypervalent iodine(iii) reagents

2019 ◽  
Vol 6 (17) ◽  
pp. 3065-3070 ◽  
Author(s):  
Yong Peng ◽  
Yuan-Yuan Jiang ◽  
Xue-Jiao Du ◽  
Da-You Ma ◽  
Luo Yang
Keyword(s):  
Radical Addition ◽  
Hypervalent Iodine ◽  
Aliphatic Aldehydes ◽  
Alkyl Radicals

Decarbonylation of aliphatic aldehydes into 1°, 2° and 3° alkyl radicals to construct C(sp3)–C(sp3) bond via radical addition and C(sp3)–O bond via the interconversion of CoII–CoIII–CoI.

A copper-catalyzed insertion of sulfur dioxide via radical coupling

2020 ◽  
Vol 56 (21) ◽  
pp. 3225-3228 ◽  
Author(s):  
Jun Zhang ◽  
Min Yang ◽  
Jin-Biao Liu ◽  
Fu-Sheng He ◽  
Jie Wu
Keyword(s):  
Sulfur Dioxide ◽  
Radical Coupling ◽  
Mild Conditions

A copper-catalyzed reaction of O-acyl oximes, DABCO·(SO2)2, and 2H-azirines is developed under mild conditions, leading to diverse tetrasubstituted β-sulfonyl N-unprotected enamines with excellent stereoselectivity and regioselectivity.

Synthesis of Indoline-2,3-diones by Radical Coupling of Indolin-2-ones with tert-Butyl Hydroperoxide

Synlett ◽  
2017 ◽  
Vol 29 (02) ◽  
pp. 215-218 ◽  
Author(s):  
Wei-Wei Ying ◽  
Wen-Ming Zhu ◽  
Hongze Liang ◽  
Wen-Ting Wei
Keyword(s):  
Coupling Reaction ◽  
Metal Catalyst ◽  
Butyl Hydroperoxide ◽  
Alkyl Radicals ◽  
Tert Butyl ◽  
Radical Coupling ◽  
Tert Butyl Hydroperoxide ◽  
Radical Coupling Reaction ◽  
Efficient Route ◽  
Novel Strategy

A novel strategy has been developed for the synthesis of indoline-2,3-diones through a metal-free radical-coupling reaction. Alkyl radicals derived from indolin-2-ones through a radical-transfer reaction combine with the tert-butylhydroperoxy radical readily generated from commercially available tert-butyl hydroperoxide to afford 3-(tert-­butylperoxy)indolin-2-one intermediates that can be further transformed into indoline-2,3-diones under air. This strategy provides a ­simple and efficient route to the construction of a C=O bond without the use of any metal catalyst or base.

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