DMSO/I2 mediated C–C bond cleavage of α-ketoaldehydes followed by C–O bond formation: a metal-free approach for one-pot esterification

2015 ◽  
Vol 13 (29) ◽  
pp. 7973-7978 ◽  
Author(s):  
Vunnam Venkateswarlu ◽  
K. A. Aravinda Kumar ◽  
Sorav Gupta ◽  
Deepika Singh ◽  
Ram A. Vishwakarma ◽  
...  
Keyword(s):  
Carboxylic Acid ◽  
Bond Cleavage ◽  
Bond Formation ◽  
One Pot ◽  
Metal Free

One-pot I2/DMSO mediated metal-free C–C bond cleavage of aryl-/heteroaryl- or aliphatic α-ketoaldehydes offering a carboxylic acid followed by esterification is presented.

An efficient method for the preparation of tert-butyl esters from benzyl cyanide and tert-butyl hydroperoxide under the metal free condition

RSC Advances ◽  
2016 ◽  
Vol 6 (104) ◽  
pp. 102023-102027 ◽  
Author(s):  
Xiuling Chen ◽  
Yan Li ◽  
Minghu Wu ◽  
Haibing Guo ◽  
Longqiang Jiang ◽  
...  
Keyword(s):  
Efficient Method ◽  
Bond Cleavage ◽  
Bond Formation ◽  
One Pot ◽  
Free Condition ◽  
Butyl Hydroperoxide ◽  
Metal Free ◽  
Tert Butyl ◽  
Butyl Esters ◽  
Tert Butyl Hydroperoxide

A novel protocol to synthesize tert-butyl esters from benzyl cyanides and tert-butyl hydroperoxide has been successfully achieved. Csp3–H bond oxidation, C–CN bond cleavage and C–O bond formation proceeded smoothly in one pot under the metal-free condition.

ChemInform Abstract: DMSO/I2Mediated C-C Bond Cleavage of α-Ketoaldehydes Followed by C-O Bond Formation: A Metal-Free Approach for One-Pot Esterification.

ChemInform ◽  
2015 ◽  
Vol 46 (46) ◽  
pp. no-no
Author(s):  
Vunnam Venkateswarlu ◽  
K. A. Aravinda Kumar ◽  
Sorav Gupta ◽  
Deepika Singh ◽  
Ram A. Vishwakarma ◽  
...  
Keyword(s):  
Bond Cleavage ◽  
Bond Formation ◽  
One Pot ◽  
Metal Free

I2/TBHP-Promoted Approach to α-Keto Esters from Trifluoromethyl β-Diketones and Alcohols via C–C Bond Cleavage

Synlett ◽  
2017 ◽  
Vol 28 (15) ◽  
pp. 2018-2023 ◽  
Author(s):  
Xiang Fang ◽  
Xueyan Yang ◽  
Tongle Shao ◽  
Jun Zhou ◽  
Chen Jin ◽  
...  
Keyword(s):  
Oxidative Coupling ◽  
Bond Cleavage ◽  
Bond Formation ◽  
Coupling Reaction ◽  
Mechanistic Studies ◽  
Metal Free ◽  
Oxidation Pathway ◽  
Keto Esters ◽  
Oxidative Coupling Reaction

A metal-free oxidative coupling reaction of trifluoromethyl β-diketones with alcohols for the synthesis of α-keto esters in good to excellent yields has been developed. Preliminary mechanistic studies suggest that an I2/TBHP promoted sequential iodination, C–C bond cleavage, C–O bond formation and oxidation pathway is involved in this reaction.

Transition-Metal-Free Catalysis for the Reductive ­Functionalization of CO2 with Amines

Synlett ◽  
2018 ◽  
Vol 29 (05) ◽  
pp. 548-555 ◽  
Author(s):  
Liang-Nian He ◽  
Xiao-Fang Liu ◽  
Xiao-Ya Li ◽  
Chang Qiao
Keyword(s):  
Transition Metal ◽  
Energy Content ◽  
Bond Formation ◽  
Energy Storage Materials ◽  
One Pot ◽  
Metal Free ◽  
Recent Developments ◽  
Electron Reduction ◽  
Reduction Of Co2 ◽  
Hierarchical Reduction

Reductive functionalization of CO2 with amines and a reductant, which combines both reduction of CO2 and C–N bond formation in one pot to produce versatile chemicals and energy-storage materials such as formamides, aminals, and methylamines that are usually derived from petroleum feedstock, would be appealing and promising. Herein, we give a brief review on recent developments in the titled CO2 chemistry by employing transition-metal-free catalysis, which can be catalogued as below according to the diversified energy content of the products, that is formamides, aminals, and methylamines being consistent with 2-, 4-, and 6-electron reduction of CO2, respectively. Notably, hierarchical reduction of CO2 with amines to afford at least two products, for example, formamides and methylamines, could be realized with the same catalyst through tuning the hydrosilane type, reaction temperature, or CO2 pressure. Finally, the opportunities and challenges of the reductive functionalization of CO2 with amines are also highlighted.1 Introduction2 2-Electron Reduction of CO2 to Formamide3 6-Electron Reduction of CO2 to Methylamine4 4-Electron Reduction of CO2 to Aminal5 Hierarchical Reduction of CO2 with Amines6 Conclusion

Metal free oxidative C C bond cleavage: Facile and one-pot tandem synthesis of benzothiadiazine-1,1-dioxides

2019 ◽  
Vol 60 (23) ◽  
pp. 1526-1529 ◽  
Author(s):  
Aniket S. Karpe ◽  
Pratima A. Sathe ◽  
Prashant Patil ◽  
Bhausaheb N. Patil ◽  
Atul C. Chaskar
Keyword(s):  
Bond Cleavage ◽  
One Pot ◽  
Metal Free ◽  
Tandem Synthesis

Visible-light-induced dual C–C bond formation via selective C(sp3)–H bond cleavage: efficient access to alkylated oxindoles from activated alkenes and simple ethers under metal-free conditions

2017 ◽  
Vol 19 (7) ◽  
pp. 1732-1739 ◽  
Author(s):  
Dong Xia ◽  
Yang Li ◽  
Tao Miao ◽  
Pinhua Li ◽  
Lei Wang
Keyword(s):  
Visible Light ◽  
Bond Cleavage ◽  
Bond Formation ◽  
Metal Free ◽  
Efficient Access ◽  
Oxidative Difunctionalization

A visible-light-induced oxidative difunctionalization of activated alkenes with simple ethersviaselective C(sp3)–H bond cleavage and dual C–C bond formation was developed.

scholarly journals Photoinduced Deaminative Borylation of Unactivated Aromatic Amines Enhanced by CO2

2021 ◽  
Author(s):  
Akira Shiozuka ◽  
Kohei Sekine ◽  
Yoichiro Kuninobu
Keyword(s):  
Aromatic Amines ◽  
Bond Cleavage ◽  
Bond Formation ◽  
Inhibitory Effect ◽  
Light Irradiation ◽  
Mechanistic Studies ◽  
Reaction Conditions ◽  
Metal Free ◽  
Stoichiometric Amount ◽  
Optimal Reaction

Herein, direct unactivated C-N borylation of aromatic amines by a photocatalyst was achieved under mild and metal-free conditions. The C-N borylation of aromatic amines with bis(pinacolato)diboron (B<sub>2</sub>pin<sub>2</sub>) proceeded in the presence of a pyrene catalyst under light irradiation (λ = 365 nm) <a>to afford desired borylated products</a> and aminoborane as a byproduct. The yield of borylated product improved under a CO<sub>2</sub> atmosphere. Reactions conducted in the presence of a stoichiometric amount of aminoborane under N<sub>2</sub> or CO<sub>2</sub> indicated that CO<sub>2</sub> reduced the inhibitory effect of aminoborane. Optimal reaction conditions were applied to a variety of aromatic amines. Mechanistic studies suggested that the C-N bond cleavage and C-B bond formation proceeded via a concerted pathway.

Transition-metal-free multinitrogenation of amides by C–C bond cleavage: a new approach to tetrazoles

2018 ◽  
Vol 54 (79) ◽  
pp. 11148-11151 ◽  
Author(s):  
Lian-Hua Li ◽  
Zhi-Jie Niu ◽  
Ying-Xiu Li ◽  
Yong-Min Liang
Keyword(s):  
Transition Metal ◽  
Bond Cleavage ◽  
Regioselective Synthesis ◽  
One Pot ◽  
New Approach ◽  
Metal Free

A metal-free brand-new one-pot multinitrogenation of amides for the chemo-, regioselective synthesis of 1,5-disubstituted tetrazoles has been developed.

scholarly journals Visible-light photoredox-catalyzed C–O bond cleavage of diaryl ethers by acridinium photocatalysts at room temperature

2020 ◽  
Vol 11 (1) ◽  
Author(s):  
Fang-Fang Tan ◽  
Xiao-Ya He ◽  
Wan-Fa Tian ◽  
Yang Li
Keyword(s):  
Carboxylic Acid ◽  
Visible Light ◽  
Room Temperature ◽  
Acid Catalysis ◽  
Bond Cleavage ◽  
Diphenyl Ether ◽  
One Pot ◽  
Diaryl Ethers ◽  
Diaryl Ether ◽  
High Bond

AbstractCleavage of C–O bonds in lignin can afford the renewable aryl sources for fine chemicals. However, the high bond energies of these C–O bonds, especially the 4-O-5-type diaryl ether C–O bonds (~314 kJ/mol) make the cleavage very challenging. Here, we report visible-light photoredox-catalyzed C–O bond cleavage of diaryl ethers by an acidolysis with an aryl carboxylic acid and a following one-pot hydrolysis. Two molecules of phenols are obtained from one molecule of diaryl ether at room temperature. The aryl carboxylic acid used for the acidolysis can be recovered. The key to success of the acidolysis is merging visible-light photoredox catalysis using an acridinium photocatalyst and Lewis acid catalysis using Cu(TMHD)2. Preliminary mechanistic studies indicate that the catalytic cycle occurs via a rare selective electrophilic attack of the generated aryl carboxylic radical on the electron-rich aryl ring of the diphenyl ether. This transformation is applied to a gram-scale reaction and the model of 4-O-5 lignin linkages.

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