595. Properties and reactions of free alkyl radicals in solution. Part IV. The direct reaction between alkyl radicals and aliphatic aldehydes

1952 ◽  
pp. 3108 ◽  
Author(s):  
E. F. P. Harris ◽  
William A. Waters
Keyword(s):  
Direct Reaction ◽  
Aliphatic Aldehydes ◽  
Alkyl Radicals

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.

Regio- and stereo-selective decarbonylative alkylative arylation of terminal alkynes with aliphatic aldehydes and arenes via dual C–H bond functionalization

2019 ◽  
Vol 6 (20) ◽  
pp. 3597-3602
Author(s):  
Yong Peng ◽  
Feng Zhang ◽  
Ting-Ting Qin ◽  
Cong-Ling Xu ◽  
Luo Yang
Keyword(s):  
Terminal Alkynes ◽  
Aliphatic Aldehydes ◽  
Bond Functionalization ◽  
Alkyl Radicals ◽  
Sugar Derivatives

Readily available linear/branched aliphatic aldehydes including sugar derivatives were oxidatively decarbonylated into 1˙, 2˙ and 3˙ alkyl radicals for the alkylative arylation of terminal alkynes via dual C–H bond functionalization.

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.

On the Significance of the Plasmal Reaction

1949 ◽  
Vol s3-90 (9) ◽  
pp. 75-86
Author(s):  
A. J. CAIN
Keyword(s):  
Mercuric Chloride ◽  
Atmospheric Oxygen ◽  
Histochemical Demonstration ◽  
The Other ◽  
Direct Reaction ◽  
Fresh Tissue ◽  
Aliphatic Aldehydes ◽  
Satisfactory Method ◽  
Plasmal Reaction ◽  
Suitable Technique

1. Two different reactions have been confused under the name ‘plasmal’. One, the true plasmal reaction, is due, as its discoverer Feulgen showed, to the liberation of higher aliphatic aldehydes from acetalphosphatides, the reaction taking place very rapidly under the influence of mercuric chloride, the products being coloured deeply with Schiff's reagent. The other reaction is due to the oxidation, by atmospheric oxygen, of double bonds in unsaturated fatty acid radicles. It is affected only slightly, if at all, by mercuric chloride, and increases with exposure of sections or pieces of tissue to atmospheric oxygen. 2. There is no completely satisfactory method for the histochemical demonstration of plasmal. Sections of fresh tissues are not usually suitable for cytological work, and fixation causes a reduction in intensity of the reaction. Also, the permissible fixatives are not all of the highest quality. Short fixation in a formaldehyde fixative (e.g. formal-calcium) followed by careful washing is probably the best, but the results should be compared with those obtained by the direct reaction of small pieces of fresh tissue. A suitable technique is described.

The Oxidation of Normal Aliphatic Aldehydes. Evidence for a chain termination by combination of acyl and alkyl radicals

1984 ◽  
Vol 326 (3) ◽  
pp. 502-504
Author(s):  
L. I. Korablev ◽  
W. Pritzkow ◽  
U. Schmidt ◽  
V. Voerckel ◽  
L. Willecke ◽  
...  
Keyword(s):  
Chain Termination ◽  
Aliphatic Aldehydes ◽  
Alkyl Radicals ◽  
A Chain

scholarly journals Fe-catalyzed Decarbonylative Alkylative Spirocyclization of N-Arylcinnamamides: Access to Alkylated 1-Azaspirocyclohexadienones

Molecules ◽  
2020 ◽  
Vol 25 (3) ◽  
pp. 432
Author(s):  
Xiang Peng ◽  
Ren-Xiang Liu ◽  
Xiang-Yan Xiao ◽  
Luo Yang
Keyword(s):  
Radical Addition ◽  
Aliphatic Aldehydes ◽  
Alkyl Radicals ◽  
Alkyl Groups ◽  
Tertiary Alkyl

For the convenient introduction of simple linear/branched alkyl groups into biologically important azaspirocyclohexadienones, a practical Fe-catalyzed decarbonylative cascade spiro-cyclization of N-aryl cinnamamides with aliphatic aldehydes to provide alkylated 1-azaspiro-cyclohexadienones was developed. Aliphatic aldehydes were oxidative decarbonylated into primary, secondary and tertiary alkyl radicals conveniently and allows for the subsequent cascade construction of dual C(sp3)-C(sp3) and C=O bonds via radical addition, spirocyclization and oxidation sequence.

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>

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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