Oxidative Coupling of Enamines and DisulfidesviaTetrabutylammonium Iodide/tert-Butyl Hydroperoxide-Mediated Intermolecular Oxidative C(sp2)S Bond Formation Under Transition Metal-Free Conditions

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.

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α-Acetoxyarone synthesis via iodine-catalyzed and tert-butyl hydroperoxide-mediateded self-intermolecular oxidative coupling of aryl ketones

Beilstein Journal of Organic Chemistry ◽

10.3762/bjoc.13.107 ◽

2017 ◽

Vol 13 ◽

pp. 1079-1084 ◽

Cited By ~ 4

Author(s):

Liquan Tan ◽

Cui Chen ◽

Weibing Liu

Keyword(s):

Oxidative Coupling ◽

Optimum Conditions ◽

Butyl Hydroperoxide ◽

Metal Free ◽

Tert Butyl ◽

Radical Intermediates ◽

Tert Butyl Hydroperoxide ◽

Aryl Ketones

We present a metal-free method for α-acetoxyarone synthesis by self-intermolecular oxidative coupling of aryl ketones using I2−tert-butyl hydroperoxide (TBHP). Under the optimum conditions, various aryl ketones gave the corresponding products in moderate to excellent yields. A series of control experiments were performed; the results suggest the involvement of radical pathways. Multiple radical intermediates were generated in situ and the overall process involved several different reactions, which proceeded self-sequentially in a single reactor. A labeling experiment using 18O-labeled H2O confirmed that the oxygen in the product was derived from TBHP, not from H2O in the TBHP solvent.

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

Synlett ◽

10.1055/s-0036-1590905 ◽

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.

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Metal-Free Oxidative Coupling of Tetrahydroisoquinolines and 3-Fluorooxindoles on Water

Synthesis ◽

10.1055/s-0039-1690213 ◽

2019 ◽

Vol 52 (03) ◽

pp. 471-478

Author(s):

Jian Ji ◽

Ling-Yan Chen ◽

Zi-Bin Qiu ◽

Xinfeng Ren ◽

Ya Li

Keyword(s):

Oxidative Coupling ◽

Reaction Conditions ◽

Butyl Hydroperoxide ◽

Metal Free ◽

Tert Butyl ◽

Tert Butyl Hydroperoxide

An efficient, metal-free oxidative coupling of tetrahydroisoquinolines and 3-fluorooxindoles on water has been developed. Using aqueous tert-butyl hydroperoxide as the oxidant, Et3N as the base, and water as the sole solvent, a variety of 3-fluorooxindoles fully substituted at the 3-position and containing a tetrahydroisoquinoline fragment has been successfully prepared in yields of up to 93% with an anti/syn stereoselectivity of up to 99:1 under very mild and safe reaction conditions.

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

RSC Advances ◽

10.1039/c6ra20966a ◽

2016 ◽

Vol 6 (104) ◽

pp. 102023-102027 ◽

Cited By ~ 4

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.

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Metal-Free Oxidative C=C Bond Cleavage of Electron-Deficient Enamines Promoted by tert-Butyl Hydroperoxide

Synlett ◽

10.1055/s-0036-1588990 ◽

2017 ◽

Vol 28 (12) ◽

pp. 1481-1485 ◽

Cited By ~ 4

Author(s):

Mehdi Adib ◽

Rahim Pashazadeh ◽

Seyed Gohari ◽

Fatemeh Shahsavari

Keyword(s):

Double Bond ◽

Bond Cleavage ◽

Bond Formation ◽

Butyl Hydroperoxide ◽

Metal Free ◽

Tert Butyl ◽

Tert Butyl Hydroperoxide ◽

New Strategy

A novel tert-butyl hydroperoxide (TBHP)-promoted oxidative C=C double-bond cleavage of enamines is described. Heating a solution of an electron-deficient enamine in chlorobenzene at 80 °C in the presence of TBHP for two hours led to cleavage of the C=C bond. This study offers a new strategy to carry out C=O double-bond formation by the use of TBHP.

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