A New Synthesis of 1,4-Thiazin-3-ones by a Novel Rearrangement of 1,4-Oxathiins

Hahn, Hoh‐Gyu; Nam, Kee Dal; Mah, Heduck; Lee, Jum Jung

doi:10.1021/jo951723h

Cited by 8 publications

(3 citation statements)

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“…The 1,4-oxathianes and -oxathiins have also been sought for access to acyclic targets [15,16] and as precursors to other heterocycles [17][18][19][20][21][22]. An oxathiin is an important component in a total synthesis of (+)-solamin [22].…”

Section: Introductionmentioning

confidence: 99%

“…The electrondeficient oxosulfine so formed can be re-captured via a hetero-Diels-Alder reaction to generate alternative 1,4-oxathiins 4-oxides [18,30]. The 1,4-oxathianes and -oxathiins have also been sought for access to acyclic targets [15,16] and as precursors to other heterocycles [17][18][19][20][21][22]. An oxathiin is an important component in a total synthesis of (+)-solamin [22].…”

Section: Introductionmentioning

confidence: 99%

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The Synthesis and Base-Induced Breakdown of Triaryl 1,4-Oxathiins—An Experimental and DFT Study

Nicol,

Sing,

Luu

et al. 2023

Molecules

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1,4-Oxathiins are valued for a breadth of bioactivities and are known commercial fungicides. This article explores a novel preparation of 2,3,6-trisubstituted 1,4-oxathiin-S,S-dioxides via the reaction of benzyl 1-alkynyl sulfones and aryl aldehydes under basic conditions. A total of 20 examples possessing exclusively a trans arrangement of the 2,3-diaryl substituents are exhibited; the products demonstrate a variation of functional groups on the aryl ring attached to the heterocyclic ring system. The preparation is hindered by the base sensitivity of the products, and a ring-opened by-product typically contaminates the reaction mixture. A DFT assessment of the overall system includes a lithium counterion and offers possible pathways for the incorporation of the aldehyde, the cyclization step and the requisite proton transfers. In addition, the DFT work reveals options for the ring opening chemistry. It appears the trans 2,3-diaryl selectivity is set during the cyclization stage of the reaction sequence. The practical work uncovers a new reaction pathway to create a family of novel 1,4-oxathiin-S,S-dioxides whereas the computational work offers an understanding of the structures and possible mechanisms involved.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

The Synthesis and Base-Induced Breakdown of Triaryl 1,4-Oxathiins—An Experimental and DFT Study

Nicol,

Sing,

Luu

et al. 2023

Molecules

View full text Add to dashboard Cite

show abstract

“…For example, 5,6-dihydro-2H-pyran-2-ones 1, which contain the -keto--sulfanyl ester functionality, have been investigated as inhibitors of HIV protease, which is essential for viral replication. 5,6 Westwood et al reported the activity of -cyano--oxoamide 2 and its derivatives as an inhibitor of an enzyme that is involved in the de novo pyrimidine biosynthesis. 7 Antirheumatic oxindoles contain a -ketoamide functionality in which the acidic enolic OH group is essential for cyclooxygenase inhibitory activity; 8 Tenidap 3 is one of the most potent oxindoles in the treatment of rheumatoid and osteoarthritis.…”

Section: Introductionmentioning

confidence: 99%