scholarly journals Allylic azides: synthesis, reactivity, and the Winstein rearrangement

2019 ◽  
Vol 17 (18) ◽  
pp. 4406-4429 ◽  
Author(s):  
Angela S. Carlson ◽  
Joseph J. Topczewski
Keyword(s):  
Synthetic Intermediates ◽  
Allylic Azides

Allylic azides are useful synthetic intermediates, the Winstein rearrangement complicates usage, and mechanistic knowledge can enable selectivity.

On the flexibility of allylic azides as synthetic intermediates

1995 ◽  
Vol 36 (48) ◽  
pp. 8737-8740 ◽  
Author(s):  
Barry M. Trost ◽  
Shon R. Pulley
Keyword(s):  
Synthetic Intermediates ◽  
Allylic Azides

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>

Synthesis of Nitrile-Bearing Quaternary Centers via an Equilibrium-Driven Transnitrilation and Anion-Relay Strategy

2019 ◽  
Author(s):  
Sebastien Alazet ◽  
Michael West ◽  
Purvish Patel ◽  
Sophie Rousseaux
Keyword(s):  
Building Blocks ◽  
One Pot ◽  
Quaternary Centers ◽  
Synthetic Intermediates

The efficient preparation of nitrile-containing building blocks is of interest due to their utility as synthetic intermediates and their prevalence in pharmaceuticals. As a result, significant efforts have been made to develop methods to access these motifs which rely on safer and non-toxic sources of CN. Herein, we report that 2-methyl-2-phenylpropanenitrile is an efficient, non-toxic, electrophilic CN source for the synthesis of nitrile-bearing quaternary centers via a thermodynamic transnitrilation and anion-relay strategy. This one-pot process leads to nitrile products resulting from the gem-difunctionalization of alkyl lithium reagents.<br>

The ammoxidation of alcohols over heterogeneous catalysts for the green synthesis of nitriles

2021 ◽  
Author(s):  
Zhijie Qi ◽  
Chaoning Hu ◽  
Youwei Zhong ◽  
Chun Cai ◽  
Guo-Ping Lu
Keyword(s):  
Green Synthesis ◽  
Heterogeneous Catalysts ◽  
Synthetic Intermediates ◽  
Novel Approaches

Nitriles are of great importance synthetic intermediates, so it is significant and appealing to develop novel approaches for green synthesis of these compounds. Compared with other synthetic strategies, the ammoxidation...

Biocatalytic approaches for enantio and diastereoselective synthesis of chiral β-nitroalcohols

2021 ◽  
Author(s):  
D. H. Sreenivasa Rao ◽  
Ayon Chatterjee ◽  
Santosh Kumar Padhi
Keyword(s):  
Bioactive Molecules ◽  
Diastereoselective Synthesis ◽  
Synthetic Intermediates

Chiral β-nitroalcohols are versatile synthetic intermediates for several pharmaceuticals, and bioactive molecules. This review describes the importance and various biocatalytic approaches for their enantio and diastereoselective synthesis.

Sustainable Electrochemical Decarboxylative Acetoxylation of Aminoacids in Batch and Continuous Flow

2021 ◽  
Author(s):  
Manuel Köckinger ◽  
Paul Hanselmann ◽  
Dominique Roberge ◽  
Piero Geotti-Bianchini ◽  
C. Oliver Kappe ◽  
...  
Keyword(s):  
Continuous Flow ◽  
Organic Molecules ◽  
Oxidative Decarboxylation ◽  
Active Ingredients ◽  
Synthetic Intermediates

Introduction of acetoxy groups to organic molecules is important for the preparation of many active ingredients and synthetic intermediates. A commonly used and attractive strategy is the oxidative decarboxylation of...

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