Taming of Thioketones: The First Asymmetric Thia‐Diels–Alder Reaction with Thioketones as Heterodienophiles

Hejmanowska, Joanna; Jasiński, Marcin; Mlostoń, Grzegorz; Albrecht, Łukasz

doi:10.1002/ejoc.201601307

Cited by 36 publications

(31 citation statements)

References 54 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Theh etero-Diels-Alder reaction of thiocarbonyls with dienes is well explored, and various 2H-thiopyrans have been obtained. [7] Remarkably,t he formation of fivemembered-ring compounds from thioketones and at hreecarbon unit has rarely been reported. [8] Donor-acceptor (D-A) cyclopropanes are one of the most frequently used three-atom building blocks.…”

mentioning

confidence: 99%

Stereospecific Reactions of Donor–Acceptor Cyclopropanes with Thioketones: Access to Highly Substituted Tetrahydrothiophenes

et al. 2017

View full text Add to dashboard Cite

Lewis-acid-catalyzed reactions of 2-substituted cyclopropane 1,1-dicarboxylates with thioketones are described. Highly substituted tetrahydrothiophenes with two adjacent quaternary carbon atoms were obtained in a stereospecific manner under mild conditions and in high yield when using AlCl as Lewis acid. Moreover, an intramolecular approach was successfully implemented to gain access to sulfur-bridged [n.2.1] bicyclic ring systems. Conversion of selenoketones, the heavier analogues, under similar conditions resulted in the formation of various tetrahydroselenophenes.

show abstract

mentioning

confidence: 99%

Stereospecific Reactions of Donor–Acceptor Cyclopropanes with Thioketones: Access to Highly Substituted Tetrahydrothiophenes

et al. 2017

View full text Add to dashboard Cite

show abstract

“…Alkyl ferrocenyl thioketones were shown to react with bis(4‐methoxyphenyl)diazomethane, and after nitrogen extrusion gave the corresponding thiiranes, which via desulfurization and demethylation were converted into ferrocifens . Hetaryl and ferrocenyl thioketones were also used as dienophiles in asymmetric thia‐Diels‐Alder reactions with enantiopure trienamines leading to optically active 5,6‐dihydro‐2 H‐ thiapyrans . Interestingly, thiochalcones react as heterodienes with the terminal C=C group of dienamines to give 3,4‐dihydro‐2 H‐ thiapyrans …”

Section: Introductionmentioning

confidence: 99%

Hetero‐Diels‐Alder Reactions of α‐Nitrosoalkenes with Ferrocenyl, Hetaryl and Cycloaliphatic Thioketones

et al. 2018

Self Cite

View full text Add to dashboard Cite

The in situ generated α-nitrosoalkenes react with ferrocenyl, hetaryl and cycloaliphatic thioketones yielding 4H-1,5,2-oxathiazines as products of the hetero-Diels-Alder reaction. These products are formed in a perfect regioselective manner. A similar reactivity is displayed by a thiochalcone (1,3-diphenylprop-2-ene-1-thione), and in that case, the [4 + 2]-cycloaddition occurs also chemoselectively and regioselectively along the C=S bond acting as a heterodienophile. The stability of the 4H-1,5,2-oxathiazines depends on the type of substituents, and in the case of ferrocenylthioketones, the diferrocenyl representa-tive is the reagent of choice. The replacement of one ferrocenyl group by an ethyl group leads to a dramatic decrease of the product stability. Sterically crowded cycloaliphatic thioketones derived from 2,2,4,4-tetramethylcyclobutane-1,3-dione are exceptional dienophiles in reactions with trifluoromethyl-substituted nitrosoalkenes, and in these cases, a remarkably stable 3trifluoromethyl-4H-1,5,2-oxathiazine derivative was obtained. For the first time, perfectly stable and non-odorous 2,2,4,4tetramethylcyclobutane-1,3-dithione was explored as an active heterodienophile for a two-fold hetero-Diels-Alder reaction.[a] Prof. Scheme 1. Typical methods for the generation of α-nitrosoalkenes 1 and their reactions with alkoxyallenes, alkenes, and diarylthioketones.

show abstract

“…In addition, asymmetric hetero-Diels–Alder reactions are of current interest [8–10]. Whereas aza- and oxa-Diels–Alder reactions are frequently applied, thia-Diels–Alder reactions are rarely reported.…”

Section: Introductionmentioning

confidence: 99%

First thia-Diels–Alder reactions of thiochalcones with 1,4-quinones

Mlostoń

Urbaniak

et al. 2018

Beilstein J. Org. Chem.

Self Cite

View full text Add to dashboard Cite

Aryl and hetaryl thiochalcones react smoothly with 1,4-quinones in THF solution at 60 °C yielding the corresponding fused 4H-thiopyrans after spontaneous dehydrogenation of the initially formed [4 + 2] cycloadducts. In general, the yields of the isolated products were high. With 5-chloro-10-hydroxy-1,4-anthraquinone, the thia-Diels–Alder reaction occurred with complete regioselectivity. In the case of the reaction of vitamin K3 (menadione) with diphenylthiochalcone, the initial cycloadduct was isolated in 37% yield.

show abstract

Taming of Thioketones: The First Asymmetric Thia‐Diels–Alder Reaction with Thioketones as Heterodienophiles

Cited by 36 publications

References 54 publications

Stereospecific Reactions of Donor–Acceptor Cyclopropanes with Thioketones: Access to Highly Substituted Tetrahydrothiophenes

Stereospecific Reactions of Donor–Acceptor Cyclopropanes with Thioketones: Access to Highly Substituted Tetrahydrothiophenes

Hetero‐Diels‐Alder Reactions of α‐Nitrosoalkenes with Ferrocenyl, Hetaryl and Cycloaliphatic Thioketones

First thia-Diels–Alder reactions of thiochalcones with 1,4-quinones

Contact Info

Product

Resources

About