[3+2]-Cycloadditions of nitrilimines with heteroaryl thioketones

Ali, Korany A.; Mlostoń, Grzegorz; Urbaniak, Katarzyna; Linden, Anthony; Heimgartner, Heinz

doi:10.1080/17415993.2017.1346103

Cited by 7 publications

(13 citation statements)

References 36 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The same group also disclosed the synthesis of 2,3‐dihydro‐1,3,4‐thiadiazoles from heteroaryl thioketones, 23 and in situ generated diarylnitrile imines ( 22 , Scheme b). Only formation of [3+2]‐cycloadducts was observed in this case . This report was in stark contrast to the observations reported for the [3+2]‐cycloaddition reaction between similar heteroaryl thioketones and diazomethane.…”

Section: [3+2]‐cycloaddition/annulation Reactions With Thiocarbonyls contrasting

confidence: 99%

“…Only formation of [3 + 2]-cycloadducts was observed in this case. [15] This report was in stark contrast to the observations reported for the [3 + 2]-cycloaddition reaction between similar heteroaryl thioketones and diazomethane. The later case afforded a very different macrocyclic heterocycle and this reactivity difference has been highlighted in the paper (inset box, Scheme 4b).…”

Section: [3 + 2]-cycloaddition Reaction Of Nitrileimines Nitrile Oxicontrasting

confidence: 76%

See 1 more Smart Citation

Recent Developments on the Synthesis of Various Sulfur‐Containing Heterocycles via [3+2]‐ and [4+2]‐Cycloaddition Reactions with Thiocarbonyls

2020

View full text Add to dashboard Cite

This minireview summarizes important collection of cycloaddition strategies that were used for the synthesis of sulfur-containing five-and six-membered heterocycles from thiocarbonyl-based synthons. Among various stepwise or concerted methods available to prepare thioheterocycles, cycloaddition reactions of thiocarbonyls in particular present an important class of reaction owing to their ability to function as super dipolarophiles and/or superdienophiles. Design and development of various reactions in recent years with thiocarbonyls have certainly superseded the general purview on this reactive synthon that it often leads to side reaction and oligomerization. This article, apart from including the advances in the known reaction manifold of thiocarbonyls, also provide updates on new developments of cycloaddition chemistry, which includes donor-acceptor (DÀ A) cyclopropanes and azaoxyallyl cation as 1,3-dipolar reaction partners. This review should serve the purpose of an important guiding tool for organic and medicinal chemist to design and develop new class of cycloaddition or related transformations with thiocarbonyls for the preparation of novel heterocycles.

show abstract

Section: [3+2]‐cycloaddition/annulation Reactions With Thiocarbonyls contrasting

confidence: 99%

Section: [3 + 2]-cycloaddition Reaction Of Nitrileimines Nitrile Oxicontrasting

confidence: 76%

Recent Developments on the Synthesis of Various Sulfur‐Containing Heterocycles via [3+2]‐ and [4+2]‐Cycloaddition Reactions with Thiocarbonyls

2020

View full text Add to dashboard Cite

show abstract

“…The ring closing metathesis (RCM) and organometallic catalysis using Pd, Rh and Ru compounds are very important tools for organic chemistry and pharmaceutical applications as they used for the preparation of active ingredients in the field of organic chemistry and pharmaceutical industry. [15][16][17][18][19][20][21][22] From these observations and in continuation of our interest of the chemistry of organo-sulfur heterocycles and sultones chemistry, [22][23][24][25][26] we reported herein an interesting preparation of a series of unsaturated sultones in addition to successful attempts of metal-catalyzed cyclopropanation on the sultone scaffold.…”

Section: Introductionmentioning

confidence: 80%

Ring closing metathesis and metal-catalyzed cyclopropanation for the preparation of sultone derivatives

Ali¹,

Metz²

2018

Arkivoc

Self Cite

View full text Add to dashboard Cite

Ring closing metathesis (RCM) using Grubbs catalyst 2 nd generation as a catalyst was applied to prepare series of novel unsaturated sultones with high yields. Many attempts, were applied for the cyclopropanation of the allylic sultones by Simmon-smith cyclopropanation using diethyl zinc/diiodomethane or Zn-Cu/diiodomethane but in each case the corresponding cyclic adduct was not formed. A novel palladium or preferably rhodiumcatalyzed cyclopropanation of unsaturated sultones with ethyl diazoacetate was achieved by the transition metal-catalyzed transfer of a CH-CO2Et unit. The reaction was applied by a portion-wise addition of ethyl diazoacetate over 6h to a mixture of the sultones and palladium(II) acetate or rhodium(II) acetate dimer under low temperature (0-20 o C). The desired products of the cyclopropanation were achieved in each case, as a single diastereomer with 33-37% yield in the allylic sultones and 10% for vinylic sultone.

show abstract

“…Based on the results of kinetic studies, R. Huisgen named them first 'superdipolarophiles' [5] and almost at the same time, his former PhD student J. Sauer coined the Based on the results of kinetic studies, R. Huisgen named them first 'superdipolarophiles' [5] and almost at the same time, his former PhD student J. Sauer coined the term 'superdienophiles' for thioketones [6]. In our very recent publications, diverse thioketones were demonstrated to act as reactive building blocks yielding five-membered S-heterocycles (or products of their secondary conversions) not only with typical 1,3-dipoles such as thiocarbonyl S-methanides [7,8], diazo alkanes [9][10][11], nitrile imines [12,13], nitrile oxides [14], etc., but also with donor-acceptor cyclopropanes in the presence of an activating Lewis acid [15]. Moreover, trienamine-mediated asymmetric hetero-Diels-Alder reactions of thioketones leading to optically active 4H-thiopyran derivatives were described [16].…”

Section: Introductionmentioning

confidence: 99%

Hetero-Diels-Alder Reactions of In Situ-Generated Azoalkenes with Thioketones; Experimental and Theoretical Studies

et al. 2021

Self Cite

View full text Add to dashboard Cite

The hetero-Diels-Alder reactions of in situ-generated azoalkenes with thioketones were shown to offer a straightforward method for an efficient and regioselective synthesis of scarcely known N-substituted 1,3,4-thiadiazine derivatives. The scope of the method was fairly broad, allowing the use of a series of aryl-, ferrocenyl-, and alkyl-substituted thioketones. However, in the case of N-tosyl-substituted cycloadducts derived from 1-thioxo-2,2,4,4-tetramethylcyclobutan-3-one and the structurally analogous 1,3-dithione, a more complicated pathway was observed. By elimination of toluene sulfinic acid, the initially formed cycloadducts afforded 2H-1,3,4-thiadiazines as final products. Advanced DFT calculations revealed that the observed high regioselectivity was due to kinetic reaction control and that the (4 + 2)-cycloadditions of sterically less unhindered thiones occurred via highly unsymmetric transition states with shorter C..S-distances (2.27–2.58 Å) and longer N..C-distances (3.02–3.57 Å). In the extreme case of the sterically very hindered 2,2,4,4-tetramethylcyclobutan-1,3-dione-derived thioketones, a zwitterionic intermediate with a fully formed C‒S bond was detected, which underwent ring closure to the 1,3,4-thiadiazine derivative in a second step. For the hypothetical formation of the regioisomeric 1,2,3-thiadiazine derivatives, the DFT calculations proposed more symmetric transition states with considerably higher energies.

show abstract

[3+2]-Cycloadditions of nitrilimines with heteroaryl thioketones

Cited by 7 publications

References 36 publications

Recent Developments on the Synthesis of Various Sulfur‐Containing Heterocycles via [3+2]‐ and [4+2]‐Cycloaddition Reactions with Thiocarbonyls

Recent Developments on the Synthesis of Various Sulfur‐Containing Heterocycles via [3+2]‐ and [4+2]‐Cycloaddition Reactions with Thiocarbonyls

Ring closing metathesis and metal-catalyzed cyclopropanation for the preparation of sultone derivatives

Hetero-Diels-Alder Reactions of In Situ-Generated Azoalkenes with Thioketones; Experimental and Theoretical Studies

Contact Info

Product

Resources

About