TBHP/n-Bu4PBr-Promoted Oxidative Cross-Dehydrogenative Coupling of Aryl Methanols: A Facile Synthesis of Symmetrical Carboxylic Anhydride Derivatives

Synlett ◽  
2017 ◽  
Vol 29 (01) ◽  
pp. 136-140
Author(s):  
Mehdi Adib ◽  
Rahim Pashazadeh
Keyword(s):  
Transition Metal ◽  
Coupling Reaction ◽  
Catalytic Amount ◽  
Facile Synthesis ◽  
Butyl Hydroperoxide ◽  
Metal Free ◽  
Tert Butyl ◽  
Dehydrogenative Coupling ◽  
Tert Butyl Hydroperoxide ◽  
Methylene Groups

A transition-metal-free oxidative cross-dehydrogenative coupling reaction has been developed for the preparation of symmetrical carboxylic anhydrides through self-coupling dual C–O bond formations of aryl methanols. In the presence of a catalytic amount of tetrabutylphosphonium bromide (TBPB) as transfer agent and aqueous tert-butyl hydroperoxide (TBHP) as oxidant and reactant, methylene groups of aryl methanols were efficiently oxidized to C=O and coupled with the peroxide oxygen from TBHP to form a diverse array of symmetrical carboxylic anhydride derivatives.

Metal-Free Synthesis of α-Aminophosphonates from Tertiary Amines and P(O)H Compounds via a Cross-Dehydrogenative Coupling Reaction

Synlett ◽  
2018 ◽  
Vol 29 (20) ◽  
pp. 2697-2700 ◽  
Author(s):  
Guo Tang ◽  
Binzhou Lin ◽  
Guozhang Lu ◽  
Rongcan Lin ◽  
Yiqun Cui ◽  
...  
Keyword(s):  
Tertiary Amine ◽  
Coupling Reaction ◽  
Transition Metal Catalysts ◽  
Tertiary Amines ◽  
Butyl Hydroperoxide ◽  
Metal Free ◽  
Tert Butyl ◽  
Dehydrogenative Coupling ◽  
Tert Butyl Hydroperoxide ◽  
Aromatic And Aliphatic Amines

The various α-aminophosphonates have been prepared from tertiary aromatic and aliphatic amines with P(O)H compounds via a tert-butyl hydroperoxide mediated cross-dehydrogenative coupling reaction, eliminating the need for transition-metal catalysts. The oxidation of tertiary amine by tert-butyl hydroperoxide generates an iminium cation intermediate. A further addition of P(O)H compound to iminium cation gives the desired product.

C(sp3)–H Peroxidation of 3-Substituted Indolin-2-ones under Metal-Free Conditions

Synlett ◽  
2017 ◽  
Vol 29 (05) ◽  
pp. 663-667 ◽  
Author(s):  
Wen-Ting Wei ◽  
Wei-Wei Ying ◽  
Wen-Ming Zhu ◽  
Zhanghua Gao ◽  
Hongze Liang
Keyword(s):  
Coupling Reaction ◽  
Butyl Hydroperoxide ◽  
Metal Free ◽  
Efficient Approach ◽  
Tert Butyl ◽  
Radical Coupling ◽  
Simple Strategy ◽  
Tert Butyl Hydroperoxide ◽  
Radical Coupling Reaction

A C(sp3)–H peroxidation of 3-substituted indolin-2-ones through radical coupling reaction has been developed under metal-free conditions. Using tert-butyl hydroperoxide both as an oxidant and as a peroxidation reagent to couple with the C(sp3)–H bonds of 3-substituted indolin-2-ones can form a new C–O bond without using any additives. This simple strategy provides a green and efficient approach to 3-peroxyindolin-2-ones in moderate to excellent yields. The resulting 3-peroxyindolin-2-ones could be further transformed into 3-hydroxy­indolin-2-ones.

Metal-Free Ammonium Iodide Catalyzed Oxidative Dehydrocoupling of Silanes with Alcohols

Synlett ◽  
2017 ◽  
Vol 28 (13) ◽  
pp. 1620-1623 ◽  
Author(s):  
Pailla Kumar ◽  
Sheng-rong Guo ◽  
Yan-qin Yuan
Keyword(s):  
Transition Metal ◽  
Oxidative Coupling ◽  
Ammonium Iodide ◽  
Reaction Conditions ◽  
Butyl Hydroperoxide ◽  
Metal Free ◽  
Tert Butyl ◽  
Tert Butyl Hydroperoxide ◽  
Free Ammonium

An ammonium iodide catalyzed direct oxidative coupling of silanes with alcohols to give various alkoxysilane derivatives was discovered. tert-Butyl hydroperoxide proved to be an efficient oxidant for this transformation. Attractive features of this protocol include its transition-metal-free nature and the mild reaction conditions.

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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