Hetero-Diels–Alder reactions of hetaryl and aryl thioketones with acetylenic dienophiles

Mloston, G.; Grzelak, Paulina; Mikina, Maciej; Linden, Anthony; Heimgartner, Heinz

doi:10.3762/bjoc.11.63

Cited by 13 publications

(8 citation statements)

References 23 publications

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“…This is usually referred to as the heteroatom effect. In the case of molecules with substituents being five-membered aromatic monocycles with a single group 16 heteroatom (furan, thiophene, selenophene, tellurophene), it is known that the heteroatom effect is responsible for changes in their properties that respond to many demands relevant to organic synthesis [ 5 – 7 ], optics [ 8 – 10 ], electronics [ 11 ], material science [ 12 ], pharmacology [ 13 ] and biology [ 14 ]. If such molecules are in solution, the surrounding solvent usually exerts an additional influence on their properties.…”

Section: Introductionmentioning

confidence: 99%

“…The resulting two series of formaldehyde and thioformaldehyde derivatives, also termed here symmetrical diheteroaryl ketones and thioketones, are interesting from both theoretical and experimental points of view. In general, they are useful for the synthesis of other important organic compounds [ 7 , 22 , 23 ]. The preparative perspective also reveals their mutual connection.…”

Section: Introductionmentioning

confidence: 99%

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Heteroatom and solvent effects on molecular properties of formaldehyde and thioformaldehyde symmetrically disubstituted with heterocyclic groups C4H3Y (where Y = O–Po)

Matczak

Domagała

2017

J Mol Model

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In this work several molecular properties of symmetrically disubstituted formaldehyde and thioformaldehyde have been studied using a quantum chemistry approach based on density functional theory. Five-membered heteroaromatic rings containing a single group 16 heteroatom were taken into account as the substituents (i.e., furan-2-yl, thiophen-2-yl, selenophen-2-yl, tellurophen-2-yl, and the experimentally as yet unknown polonophen-2-yl). For the resulting ten formaldehyde and thioformaldehyde derivatives, the geometry, energetics, frontier molecular orbitals, dipole moment and polarizability of their molecules were examined in order to establish the effect of ring heteroatom on these properties. Furthermore, these properties were also determined for the molecules in three solvents of low polarity (benzene, chloroform, and dichloromethane) in order to expand our study to include solvent effects. The dipole moment and polarizability of the investigated molecules show regular variations when the ring heteroatom descends through group 16 and the solvent polarity grows. The heteroatom and/or solvent effects on the part of the studied properties are, however, more complex. An attempt is made to rationalize the observed variations in the molecular properties. The conformational behavior of the investigated molecules was also explored and the conformationally weighted values of dipole moment and polarizability are presented. Graphical abstractSome molecular properties of symmetrically disubstituted formaldehyde and thioformaldehyde Electronic supplementary materialThe online version of this article (doi:10.1007/s00894-017-3435-4) contains supplementary material, which is available to authorized users.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Heteroatom and solvent effects on molecular properties of formaldehyde and thioformaldehyde symmetrically disubstituted with heterocyclic groups C4H3Y (where Y = O–Po)

Matczak

Domagała

2017

J Mol Model

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“…Finally, the molecular structures of 9c and 9g were u biguously confirmed by X-ray analyses (Figure 2). Quite unexpectedly, two other aromatic thioketones, namely 2,3,6,7-dibenzoc heptene-1-thione (1m) and its 10,11-dihydro analogue (1n), which have been appli our earlier studies focused on hetero-Diels-Alder reactions [35], failed to react with 7a after 3 days at rt and no discoloration of the blue solutions was observed after that t Ferrocenyl-substituted thioketones 1e-h reacted similarly to aromatic repres tives, and the reactions carried out at rt in CH2Cl2 with 8a, applied as a precursor o reactive azoalkene 7a, led to the ferrocenyl substituted 1,3,4-thiadiazine deriva (9i,k,m,o) in 39-56% yield (Scheme 5). A similar course of the studied reactions, reg lectively leading to cycloadducts 9j, l, n, and 9p, was observed with the N-benzoyl tionalized azoalkene 7b.…”

Section: Experimental Workmentioning

confidence: 97%

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

et al. 2021

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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.

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“…Heimgartner and co-workers extensively studied [4 + 2]-cycloaddition reactions of various heteroaryl thioketones for the synthesis of interesting class of fused thiacycles. [45] For example, reaction of thiobenzophenone and dimethylacetylene dicarboxylate first afforded the fused scaffold 95, which then converted to more stable product 96 through 1,3-H-shift (Scheme 26a). Heteroaryl thiocarbonyl 97 also afforded similar reaction to compound 98 (Scheme 26b).…”

Section: Aryl and Heteroaryl Thioketones As Heterodienes (4π-system) mentioning

confidence: 99%

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

2020

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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.

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Hetero-Diels–Alder reactions of hetaryl and aryl thioketones with acetylenic dienophiles

Cited by 13 publications

References 23 publications

Heteroatom and solvent effects on molecular properties of formaldehyde and thioformaldehyde symmetrically disubstituted with heterocyclic groups C4H3Y (where Y = O–Po)

Heteroatom and solvent effects on molecular properties of formaldehyde and thioformaldehyde symmetrically disubstituted with heterocyclic groups C4H3Y (where Y = O–Po)

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

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

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