Stereoselective Aminoiodination of Activated Alkynes with Organoiodine(III) Reagents and Amines via Multiple-Site Functionalization: Access to Iodinated Enamines and N-Aryl Indoles

2019 ◽  
Author(s):  
sagar arepally ◽  
Narenderreddy Katta ◽  
Ajoy Chamuah ◽  
Sharada Duddu. S
Keyword(s):  
Hydrogen Bonding ◽  
Steric Hindrance ◽  
Single Step ◽  
Multiple Site ◽  
Aryl Group ◽  
Mild Conditions ◽  
Reaction Proceeds ◽  
Activated Alkynes ◽  
Acidic Conditions ◽  
High Stereoselectivity

<p>A stereoselective aminoiodination of activated alkynes with PhI(OAc)<sub>2</sub> and amines <i>via</i> multiple-site functionalization to afford (<i>Z</i>)diethyl 2-(diphenylamino)-3-iodomaleate derivatives with superior yields has been described. The key feature of this reaction is the incorporation of iodide and aryl group concurrently in the same molecule in a stereoselective manner by employing PhI(OAc)<sub>2</sub> as electrophilic reagent as well as iodide and aryl group source. The high stereoselectivity of the reaction can be explained based on the structure of the possible intermediates, the conformations of which controlled by the hydrogen bonding, steric hindrance and electrostatic attractions. This reaction proceeds under mild conditions, providing various dialkyl 2-(diphenylamino)-3-iodomaleates by a single operation starting from activated alkynes. The robustness of our strategy is revealed by making of bis (dialkyl 2-(diphenylamino)-3-iodomaleate) derivatives involving formation of four new C-N bonds and two C-I bonds with a single step. The synthesized inactive 3° enamines (dialkyl 2-(diphenylamino)-3-iodomaleates) could be further transformed into highly substituted indoles via Pd catalyzed C-H and C-I activation under non-acidic conditions. </p><br>

Stereoselective Aminoiodination of Activated Alkynes with Organoiodine(III) Reagents and Amines via Multiple-Site Functionalization: Access to Iodinated Enamines and N-Aryl Indoles

2018 ◽  
Author(s):  
sagar arepally ◽  
Ajoy Chamuah ◽  
Sharada Duddu. S
Keyword(s):  
Hydrogen Bonding ◽  
Steric Hindrance ◽  
Single Step ◽  
Multiple Site ◽  
Aryl Group ◽  
Mild Conditions ◽  
Reaction Proceeds ◽  
Activated Alkynes ◽  
Acidic Conditions ◽  
High Stereoselectivity

<p>A stereoselective aminoiodination of activated alkynes with PhI(OAc)<sub>2</sub> and amines <i>via</i> multiple-site functionalization to afford (<i>Z</i>)diethyl 2-(diphenylamino)-3-iodomaleate derivatives with superior yields has been described. The key feature of this reaction is the incorporation of iodide and aryl group concurrently in the same molecule in a stereoselective manner by employing PhI(OAc)<sub>2</sub> as electrophilic reagent as well as iodide and aryl group source. The high stereoselectivity of the reaction can be explained based on the structure of the possible intermediates, the conformations of which controlled by the hydrogen bonding, steric hindrance and electrostatic attractions. This reaction proceeds under mild conditions, providing various dialkyl 2-(diphenylamino)-3-iodomaleates by a single operation starting from activated alkynes. The robustness of our strategy is revealed by making of bis (dialkyl 2-(diphenylamino)-3-iodomaleate) derivatives involving formation of four new C-N bonds and two C-I bonds with a single step. The synthesized inactive 3° enamines (dialkyl 2-(diphenylamino)-3-iodomaleates) could be further transformed into highly substituted indoles via Pd catalyzed C-H and C-I activation under non-acidic conditions. </p><br>

Stereoselective Aminoiodination of Activated Alkynes with Organoiodine(III) Reagents and Amines via Multiple-Site Functionalization: Access to Iodinated Enamines and N-Aryl Indoles

2019 ◽  
Author(s):  
sagar arepally ◽  
Narenderreddy Katta ◽  
Ajoy Chamuah ◽  
Sharada Duddu. S
Keyword(s):  
Hydrogen Bonding ◽  
Steric Hindrance ◽  
Single Step ◽  
Multiple Site ◽  
Aryl Group ◽  
Mild Conditions ◽  
Reaction Proceeds ◽  
Activated Alkynes ◽  
Acidic Conditions ◽  
High Stereoselectivity

<p>A stereoselective aminoiodination of activated alkynes with PhI(OAc)<sub>2</sub> and amines <i>via</i> multiple-site functionalization to afford (<i>Z</i>)diethyl 2-(diphenylamino)-3-iodomaleate derivatives with superior yields has been described. The key feature of this reaction is the incorporation of iodide and aryl group concurrently in the same molecule in a stereoselective manner by employing PhI(OAc)<sub>2</sub> as electrophilic reagent as well as iodide and aryl group source. The high stereoselectivity of the reaction can be explained based on the structure of the possible intermediates, the conformations of which controlled by the hydrogen bonding, steric hindrance and electrostatic attractions. This reaction proceeds under mild conditions, providing various dialkyl 2-(diphenylamino)-3-iodomaleates by a single operation starting from activated alkynes. The robustness of our strategy is revealed by making of bis (dialkyl 2-(diphenylamino)-3-iodomaleate) derivatives involving formation of four new C-N bonds and two C-I bonds with a single step. The synthesized inactive 3° enamines (dialkyl 2-(diphenylamino)-3-iodomaleates) could be further transformed into highly substituted indoles via Pd catalyzed C-H and C-I activation under non-acidic conditions. </p><br>

Single-Step Dual Functionalization: One-Pot Bromination-Cross-Dehydrogenative Esterification of Hydroxy Benzaldehydes with CCl3Br – A Comparison with Selectfluor

Synlett ◽  
2019 ◽  
Vol 30 (14) ◽  
pp. 1713-1718 ◽  
Author(s):  
Ranadeep Talukdar
Keyword(s):  
Phenolic Compounds ◽  
Aldehyde Group ◽  
Single Step ◽  
Molecular Bromine ◽  
One Pot ◽  
Blue Led ◽  
Aryl Ring ◽  
Mild Conditions ◽  
Reaction Proceeds ◽  
Phenolic Esters

Bromination of phenolic compounds without directly using molecular bromine possesses much importance. In this article an IrIII/CCl3Br-assisted single-step double functionalization of hydroxy benzaldehydes is reported. It involves simultaneous esterification of the aldehyde group and bromination of the aryl ring of phenolic aldehydes in one-pot. The reaction proceeds under mild conditions in the presence of 445 nm blue LED light to obtain highly functionalized bromo hydroxy benzoates in moderate to good yields. In comparison, Selectfluor as an oxidant gives only non-bromo phenolic esters.

scholarly journals Broad scope gold(i)-catalysed polyenyne cyclisations for the formation of up to four carbon–carbon bonds

2017 ◽  
Vol 15 (10) ◽  
pp. 2163-2167 ◽  
Author(s):  
Zhouting Rong ◽  
Antonio M. Echavarren
Keyword(s):  
Single Step ◽  
Simultaneous Formation ◽  
Broad Scope ◽  
Carbon Carbon Bonds ◽  
Carbon Bonds ◽  
First Time ◽  
High Stereoselectivity

The polycyclisation of polyeneynes catalyzed by gold(i) has been extended for the first time to the simultaneous formation of up to four carbon–carbon bonds, leading to steroid-like molecules with high stereoselectivity in a single step with low catalyst loadings.

scholarly journals Nickel-Catalyzed Asymmetric Reductive Cross-Coupling of α-Chloroesters with (Hetero)Aryl Iodides

2021 ◽  
Author(s):  
Travis DeLano ◽  
Sara Dibrell ◽  
Caitlin R. Lacker ◽  
Adam Pancoast ◽  
Kelsey Poremba ◽  
...  
Keyword(s):  
Cross Coupling ◽  
Mild Conditions ◽  
Aryl Iodides ◽  
Reaction Proceeds

An asymmetric reductive cross-coupling of α-chloroesters and (hetero)aryl iodides is reported. This nickel-catalyzed reaction proceeds with a chiral BiOX ligand under mild conditions, affording α-arylesters in good yields and enantioselectivities....

scholarly journals Effects of alkanolamine solvents on the aggregation states of reactive dyes in concentrated solutions and the properties of the solutions

RSC Advances ◽  
2021 ◽  
Vol 11 (18) ◽  
pp. 10929-10934
Author(s):  
Chuangui Cao ◽  
Zhihui Zhao ◽  
Yong Qi ◽  
Hui Peng ◽  
Kuanjun Fang ◽  
...  
Keyword(s):  
Hydrogen Bonding ◽  
Steric Hindrance ◽  
Reactive Dyes ◽  
Concentrated Solutions ◽  
Weak Hydrogen Bonding ◽  
Dye Aggregation

The solvent, DEA, reduces the dye aggregation that may be caused by the weak hydrogen bonding and relatively smaller steric hindrance effect.

A metal-free radical cascade reaction of phosphine oxides with 2-aryloxy phenylacetylenes to assemble diphosphonyl xanthene derivatives

2021 ◽  
Author(s):  
Tao Fan ◽  
Yan Liu ◽  
Caina Jiang ◽  
Yanli Xu ◽  
Yan-Yan Chen
Keyword(s):  
Free Radical ◽  
Transition Metal ◽  
Cascade Reaction ◽  
Phosphine Oxides ◽  
Metal Free ◽  
Mild Conditions ◽  
Xanthene Derivatives ◽  
Reaction Proceeds ◽  
Radical Cascade

A radical cascade reaction of 2-aryloxy phenylacetylene with phosphine oxides promoted by K2S2O8 was developed, provided diphosphonyl xanthenes as products. This reaction proceeds under transition metal-free and mild conditions with...

scholarly journals The Energetic Viability of Δ1-Piperideine Dimerization in Lysine-derived Alkaloid Biosynthesis

Metabolites ◽  
2018 ◽  
Vol 8 (3) ◽  
pp. 48 ◽  
Author(s):  
Hajime Sato ◽  
Masanobu Uchiyama ◽  
Kazuki Saito ◽  
Mami Yamazaki
Keyword(s):  
Density Functional ◽  
Indole Alkaloid ◽  
Alkaloid Biosynthesis ◽  
Functional Theory ◽  
The Density Functional Theory ◽  
Reaction Proceeds ◽  
Acidic Conditions ◽  
Dimerization Reaction ◽  
Available Information ◽  
Skeleton Formation

Lys-derived alkaloids widely distributed in plant kingdom have received considerable attention and have been intensively studied; however, little is known about their biosynthetic mechanisms. In terms of the skeleton formation, for example, of quinolizidine alkaloid biosynthesis, only the very first two steps have been identified and the later steps remain unknown. In addition, there is no available information on the number of enzymes and reactions required for their skeletal construction. The involvement of the Δ 1 -piperideine dimerization has been proposed for some of the Lys-derived alkaloid biosyntheses, but no enzymes for this dimerization reaction have been reported to date; moreover, it is not clear whether this dimerization reaction proceeds spontaneously or enzymatically. In this study, the energetic viability of the Δ 1 -piperideine dimerizations under neutral and acidic conditions was assessed using the density functional theory computations. In addition, a similar type of reaction in the dipiperidine indole alkaloid, nitramidine, biosynthesis was also investigated. Our findings will be useful to narrow down the candidate genes involved in the Lys-derived alkaloid biosynthesis.

Bromotrifluoromethane: A Useful Reagent for Hydrotrifluoromethylation of Alkenes and Alkynes

Synlett ◽  
2018 ◽  
Vol 29 (08) ◽  
pp. 1028-1032 ◽  
Author(s):  
Xing Zheng ◽  
Xingang Zhang ◽  
Yu-Yan Ren
Keyword(s):  
Visible Light ◽  
Organic Synthesis ◽  
Functional Group ◽  
Mild Conditions ◽  
Industrial Material ◽  
Reaction Proceeds

Bromotrifluoromethane (CF3Br) is a simple, inexpensive and abundant industrial material employed as a trifluoromethylating reagent. However, only limited strategies using CF3Br as a fluorine source are reported. Herein, we describe a visible-light-induced hydrotrifluoromethylation of alkenes and alkynes with CF3Br. The reaction proceeds under mild conditions with good functional group tolerance, providing a new route for the application of BrCF3 in organic synthesis.

scholarly journals A Photochemical Strategy for Carbon Isotope Exchange with CO2

2020 ◽  
Author(s):  
Victor Babin ◽  
Alex Talbot ◽  
Alexandre Labiche ◽  
Gianluca Destro ◽  
Antonio Del Vecchio ◽  
...  
Keyword(s):  
Carbon Isotope ◽  
Isotope Exchange ◽  
Thermal Conditions ◽  
Single Step ◽  
Structural Modifications ◽  
Mild Conditions ◽  
Stark Contrast ◽  
Acetic Acids

A novel photocatalytic approach for carbon isotope exchange is reported. Utilizing [<sup>13</sup>C]CO<sub>2</sub> as primary C1 sources, this protocol allows the insertion of the desired carbon isotope into phenyl acetic acids without the need of structural modifications or pre-functionalization, in one single step. The exceptionally mild conditions required for this traceless transformation are in stark contrast with previous methods requiring the use of harsh thermal conditions.

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