scholarly journals Insights into the nucleophilic substitution of pyridine at an unsaturated carbon center

RSC Advances ◽  
2021 ◽  
Vol 11 (39) ◽  
pp. 24238-24246
Author(s):  
Pan Du ◽  
Jiyang Zhao ◽  
Shanshan Liu ◽  
Zhen Yue
Keyword(s):  
Nucleophilic Substitution ◽  
Vinyl Carbon ◽  
Carbon Centers

The nucleophilic substitution of carbonyl, imidoyl, and vinyl carbon centers with pyridine or halides is investigated in this paper.

Nucleophilic Substitution at the Imidoyl Carbon Atom: Intermediate Mechanistic and Reactivity Behavior between Carbonyl and Vinyl Carbon Substitution

2001 ◽  
Vol 123 (10) ◽  
pp. 2326-2333 ◽  
Author(s):  
Hong Guang Li ◽  
Chang Kon Kim ◽  
Bon-Su Lee ◽  
Chan Kyung Kim ◽  
Soon Ki Rhee ◽  
...  
Keyword(s):  
Carbon Atom ◽  
Nucleophilic Substitution ◽  
Vinyl Carbon ◽  
Carbon Substitution

Cascade CuH-Catalyzed Conversion of Alkynes to Enantioenriched 1,1-Disubstituted Products

2019 ◽  
Author(s):  
De-Wei Gao ◽  
Yang Gao ◽  
Huiling Shao ◽  
Tian-Zhang Qiao ◽  
Xin Wang ◽  
...  
Keyword(s):  
Organic Synthesis ◽  
Medicinal Chemistry ◽  
Proteasome Inhibitors ◽  
Building Blocks ◽  
Unique Role ◽  
Efficient Strategy ◽  
Carbon Centers ◽  
Rapid Access ◽  
Cascade Catalysis ◽  
Privileged Scaffolds

Enantioenriched <i>α</i>-aminoboronic acids play a unique role in medicinal chemistry and have emerged as privileged pharmacophores in proteasome inhibitors. Additionally, they represent synthetically useful chiral building blocks in organic synthesis. Recently, CuH-catalyzed asymmetric alkene hydrofunctionalization has become a powerful tool to construct stereogenic carbon centers. In contrast, applying CuH cascade catalysis to achieve reductive 1,1-difunctionalization of alkynes remains an important, but largely unaddressed, synthetic challenge. Herein, we report an efficient strategy to synthesize <i>α</i>-aminoboronates <i>via </i>CuH-catalyzed hydroboration/hydroamination cascade of readily available alkynes. Notably, this transformation selectively delivers the desired 1,1-heterodifunctionalized product in favor of alternative homodifunctionalized, 1,2-heterodifunctionalized, or reductively monofunctionalized byproducts, thereby offering rapid access to these privileged scaffolds with high chemo-, regio- and enantioselectivity.<br>

Modular, Stereocontrolled Cβ–H/Cα–C Activation of Alkyl Carboxylic Acids

2019 ◽  
Author(s):  
Ming Shang ◽  
Karla S. Feu ◽  
Julien C. Vantourout ◽  
Lisa M. Barton ◽  
Heather L. Osswald ◽  
...  
Keyword(s):  
Carboxylic Acid ◽  
Heterocyclic Compounds ◽  
Cross Coupling ◽  
Building Blocks ◽  
Enantioselective Synthesis ◽  
Carbon Centers ◽  
Drug Candidates ◽  
Rapid Diversification ◽  
Directing Group ◽  
Compound Series

<div> <div> <div> <p>The union of two powerful transformations, directed C–H activation and decarboxylative cross-coupling, for the enantioselective synthesis of vicinally functionalized alkyl, carbocyclic, and heterocyclic compounds is described. Starting from simple carboxylic acid building blocks, this modular sequence exploits the residual directing group to access more than 50 scaffolds that would be otherwise extremely difficult to prepare. The tactical use of these two transformations accomplishes a formal vicinal difunctionalization of carbon centers in a way that is modular and thus amenable to rapid diversity incorporation. A simplification of routes to known preclinical drug candidates is presented along with the rapid diversification of an antimalarial compound series. </p> </div> </div> </div>

The Synthesis of New Selenium-containing Heterocycles by the Oxidation Reaction of 2,4-Diaryltetrahydro-4H-selenochromenes

2020 ◽  
Vol 24 (15) ◽  
pp. 1663-1668
Author(s):  
Dmitriy Yurievich Direnko ◽  
Boris Ivanovich Drevko ◽  
Yaroslav Borisovich Drevko
Keyword(s):  
Nucleophilic Substitution ◽  
Chlorine Atom ◽  
Oxidation Reaction ◽  
Heterocyclic Fragment ◽  
Oxidative Aromatization

We have explored the reactions of tetrahydro-4H-selenochromenes in the presence of phosphoric pentachloride, and synthesized new condensate aroylbenzoselenophenes. During the reactions, tetrahydro-4H-selenochromenes with phosphoric pentachloride underwent oxidative aromatization and nucleophilic substitution for a chlorine atom of one of the protons in the alicyclic fragment. Also, the narrowing of the heterocyclic fragment occurred as in synthesized selenium-containing compounds earlier transformed into the corresponding condensate aroylbenzoselenophenes.

On the Reaction of 2,5-Dihydroxy-[1,4]-benzoquinone with Diamines – Strain-induced Reactivity Effects

2020 ◽  
Vol 24 ◽  
Author(s):  
Hubert Hettegger ◽  
Andreas Hofinger ◽  
Thomas Rosenau
Keyword(s):  
Nucleophilic Substitution ◽  
Product Structure ◽  
Carbonyl Groups ◽  
Reaction Products ◽  
Double Bonds ◽  
Oh Groups ◽  
Natural Geometry ◽  
Quinoid Structure ◽  
Bond Localization

: The regioselectivity of the reaction of 2,5-dihydroxy-[1,4]-benzoquinone (DHBQ) with diamines could not be explained satisfactorily so far. In general, the reaction products can be derived from the tautomeric ortho-quinoid structure of a hypothetical 4,5-dihydroxy-[1,2]-benzoquinone. However, both aromatic and aliphatic 1,2-diamines form in some cases phenazines, formally by diimine formation on the quinoid carbonyl groups, and in other cases the corresponding 1,2- diamino-[1,2]-benzoquinones, by nucleophilic substitution of the OH groups, the regioselectivity apparently not following any discernible pattern. The reactivity was now explained by an adapted theory of strain-induced bond localization (SIBL). Here, the preservation of the "natural" geometry of the two quinoid C–C double bonds (C3=C4 and C5=C6) as well as the N–N distance of the co-reacting diamine are crucial. A decrease of the annulation angle sum (N–C4–C5 + C4–C5–N) is tolerated well and the 4,5-diamino-ortho-quinones, having relatively short N–N spacings are formed. An increase in the angular sum is energetically unfavorable, so that diamines with a larger N–N distance afford the corresponding ortho-quinone imines. Thus, for the reaction of DHBQ with diamines, exact predictions of the regioselectivity, and the resulting product structure, can be made on the basis of simple computations of bond spacings and product geometries.

Sign in / Sign up

Export Citation Format

Share Document