Metal-Free Addition of Boronic Acids to Silylnitronates

Synlett ◽  
2020 ◽  
Vol 31 (09) ◽  
pp. 856-860
Author(s):  
Laurent El Kaïm ◽  
Mansour Dolé Kerim ◽  
Pakoupati Boyode ◽  
Julian Garrec
Keyword(s):  
Reaction Mechanism ◽  
Double Bond ◽  
Boronic Acids ◽  
Dft Study ◽  
Metal Free ◽  
Nitro Derivatives ◽  
Oxime Derivatives ◽  
Nitrogen Double Bond ◽  
First Time ◽  
Aryl Transfer

We report for the first time a metal-free addition of boronic acids to silylnitronates to afford oxime derivatives through aryl transfer on the carbon nitrogen double bond. A reaction mechanism has been proposed in relation with a DFT study on the key aryl transfer. This arylation process is effective for cycloalkenyl nitro derivatives leading to oximes that may be oxidatively converted into 3-arylisoxazole derivatives.

scholarly journals Continuous-flow synthesis of primary amines: Metal-free reduction of aliphatic and aromatic nitro derivatives with trichlorosilane

2016 ◽  
Vol 12 ◽  
pp. 2614-2619 ◽  
Author(s):  
Riccardo Porta ◽  
Alessandra Puglisi ◽  
Giacomo Colombo ◽  
Sergio Rossi ◽  
Maurizio Benaglia
Keyword(s):  
Continuous Flow ◽  
Reaction Times ◽  
Nitro Compounds ◽  
Primary Amines ◽  
Flow Conditions ◽  
Metal Free ◽  
Nitro Derivatives ◽  
Aromatic Nitro ◽  
High Yields ◽  
First Time

The metal-free reduction of nitro compounds to amines mediated by trichlorosilane was successfully performed for the first time under continuous-flow conditions. Aromatic as well as aliphatic nitro derivatives were converted to the corresponding primary amines in high yields and very short reaction times with no need for purification. The methodology was also extended to the synthesis of two synthetically relevant intermediates (precursors of baclofen and boscalid).

Insights into the NHC-catalyzed cascade Michael/aldol/lactamization reaction: mechanism and origin of stereoselectivity

2018 ◽  
Vol 5 (13) ◽  
pp. 2065-2072 ◽  
Author(s):  
Yang Wang ◽  
Shou-Ren Zhang ◽  
Yanyan Wang ◽  
Ling-Bo Qu ◽  
Donghui Wei
Keyword(s):  
Reaction Mechanism ◽  
Dft Study ◽  
First Time

A DFT study of the NHC-catalyzed cascade Michael/aldol/lactamization reaction has been performed for the first time.

A Novel Scheme for the Synthesis of 21-Acetoxypregna-1,4,9(11)-triene- 17α,21-diol-3,20-dione from 9α-Hydroxyandrostenedione

2020 ◽  
Vol 16 (5) ◽  
pp. 606-610
Author(s):  
Nguyen T. Diep ◽  
Luu D. Huy
Keyword(s):  
Double Bond ◽  
Chemical Synthesis ◽  
Economic Efficiency ◽  
Final Stage ◽  
Side Chain ◽  
Entire Process ◽  
Drug Synthesis ◽  
First Time

Background: Vietnam currently imports up to 90% of the pharmaceuticals it consumes and 100% of the steroid-based pharmaceuticals. The ability for efficient chemical synthesis of the steroids could create commercial opportunities to address this issue. Synthesis of 21-acetoxypregna-1,4,9(11)- triene-17α,21-diol-3,20-dione is considered a key intermediate in the scheme of steroidal drug synthesis. Previous synthesis attempts of such steroids (corticoids) introduce a double bond at C-1(2) in the final stage of synthesis, which delivers a poor yield and reduces the economic efficiency of the process. Objective: To study and develop a novel and effective method for the synthesis of 21-acetoxypregna- 1,4,9(11)-triene-17α,21-diol-3,20-dione. Methods: Using 9α-hydroxyandrostenedione as a substrate chemical synthesis was performed as follows: pregnane side chain construction at C-17 (acetylene method), introduction of C-1(2) double bond (using SeO2), epimerization of C-17 (via 17-ONO2 ester) and Stork’s iodination. Results: 21-acetoxypregna-1,4,9(11)-triene-17α,21-diol-3,20-dione was prepared from 9α- hydroxyandrostenedione with an improved yield compared to previous attempts. Conclusion: Here, 21-acetoxypregna-1,4,9(11)-triene-17α,21-diol-3,20-dione has been synthesized from 9α-hydroxyandrostenedione based on a novel, effective and commercially feasible scheme. The introduction of the C-1(2) double bond at an earlier stage of the synthesis has increased the economic efficiency of the entire process. For the first time, the indirect epimerization mechanism has been clarified along with the configuration of the C-17 stereo-center which has been confirmed using NOESY data.

scholarly journals A computational study for the reaction mechanism of metal-free cyanomethylation of aryl alkynoates with acetonitrile

RSC Advances ◽  
2021 ◽  
Vol 11 (30) ◽  
pp. 18246-18251
Author(s):  
Selçuk Eşsiz
Keyword(s):  
Density Functional Theory ◽  
Reaction Mechanism ◽  
Density Functional ◽  
Computational Study ◽  
Coupled Cluster ◽  
Functional Theory ◽  
Metal Free ◽  
Coupled Cluster Methods ◽  
High Level ◽  
Cluster Methods

A computational study of metal-free cyanomethylation and cyclization of aryl alkynoates with acetonitrile is carried out employing density functional theory and high-level coupled-cluster methods, such as [CCSD(T)].

Configuration stability at the carbon-nitrogen double bond

1962 ◽  
Vol 3 (26) ◽  
pp. 1269-1274 ◽  
Author(s):  
D.Y. Curtin ◽  
C.G. McCarty
Keyword(s):  
Double Bond ◽  
Nitrogen Double Bond

Electrochemical Oxidative Cyclization of Alkenes, Boronic Acids, and Dichalcogenides to Access Chalcogenated Boronic Esters and 1,3-Diols

2021 ◽  
Author(s):  
Changfeng Huang ◽  
Jijing Hu ◽  
Guangxian Chen ◽  
Minjian Wu ◽  
Hua Cao ◽  
...  
Keyword(s):  
Boronic Acids ◽  
Oxidative Cyclization ◽  
Environmentally Benign ◽  
Allylic Alcohols ◽  
Efficient Manner ◽  
Metal Free ◽  
Boronic Esters

A sustainable, environmentally benign electrochemical oxidative three-component cyclization of allylic alcohols, boronic acids, and dichalcogenides under metal-free and oxidant-free conditions has been developed, which provides an efficient manner for the...

Brønsted Acid-Catalyzed Solvent-Controlled Regioselective Hydrothiolation and Diastereoselective Cascade Cyclization of Dienes

2021 ◽  
Author(s):  
Kai Ji ◽  
Ka Lu ◽  
Jie Huang ◽  
Zi-Hao Li ◽  
Tong-Mei Ding ◽  
...  
Keyword(s):  
Free Atom ◽  
Bronsted Acid ◽  
Brønsted Acid ◽  
Metal Free ◽  
Cascade Cyclization ◽  
Brönsted Acid ◽  
Acid Catalyzed ◽  
First Time

A highly regio- and diastereo-selective Brønsted acid-catalyzed tandem hydrothiolation/Friedel-Crafts reaction of linear 1,3-dienes has been developed for the first time, which provides a metal-free, atom-economic and concise way of constructing...

Relativistic DFT Study on the Reaction Mechanism of Second-Row Transition Metal Ru with CO2

2006 ◽  
Vol 110 (10) ◽  
pp. 3552-3558 ◽  
Author(s):  
Xian-Yang Chen ◽  
Yi-Xin Zhao ◽  
Shu-Guang Wang
Keyword(s):  
Reaction Mechanism ◽  
Transition Metal ◽  
Dft Study ◽  
Relativistic Dft
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