Chemistry of .alpha.,.beta.-unsaturated thione dimers. 2. Reactions of thiochalcones and 2-arylidene-1-thiotetralones with some olefins and the parent ketones of the thiones

Karakasa, Takayuki; Motoki, Shinichi

doi:10.1021/jo01337a029

Cited by 47 publications

(9 citation statements)

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“…It is nevertheless complete and gives the expected 2,4,5-trisubstituted 3,4-dihydro-2H-thiopyrans in good yields with high regio-and good diastereoselectivities. The preference for the endo adducts is in line with previous results obtained with a,b-unsaturated thi- oketones, [42,43] dithioesters, [44,45] or thioamides. [33] The fact that the diastereoselectivity is even higher than in most of the previous cases [33,[42][43][44][45] is certainly due to the restrictions imposed by the bulky ruthenium complex.…”

Section: Discussionsupporting

confidence: 91%

Ruthenium Complexes of Thiocinnamaldehydes: Synthesis, Structure, and [4+2]‐Cycloaddition Reactions

Schenk

Beucke

Burzlaff

et al. 2006

Chemistry A European J

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Ruthenium hydrogensulfido complexes [CpRu(P-P)(SH)] ((P-P)=Ph(2)PCH(2)PPh(2) (dppm), Ph(2)PC(2)H(4)PPh(2) (dppe)) were obtained from the corresponding chloro complexes by Cl/SH exchange. Condensation with a range of cinnamaldehydes gave thiocinnamaldehyde complexes [CpRu(P-P)(S=CH-CR(2)=CHR(1))]PF(6) (R(1)=C(6)H(4)X, R(2)=H, Me, X=H, OMe, NMe(2), Cl, NO(2)) as highly-colored crystalline compounds. The thiocinnamaldehyde complexes undergo [4+2]-cycloaddition reactions with vinyl ethers CH(2)=CHOR(3) (R(3)=Et, Bu) and styrenes H(2)C=CHC(6)H(4)Y (Y=H, Me, OMe, Cl, Br, NO(2)) to give complexes of 2,4,5-trisubstituted 3,4-dihydro-2H-thiopyrans as mixtures of two diastereoisomers. The rate of addition of para-substituted styrenes H(2)C=CHC(6)H(4)Y to [CpRu(dppm)(S=CH-CH=CHPh)]PF(6) increases in the series Y=NO(2), Br, Cl, H, Me, OMe, indicating that the cycloaddition is dominated by the HOMO(dienophile)-LUMO(diene) interaction. The strained dienophiles norbornadiene and norbornene also add, giving ruthenium complexes of 3-thia-tricyclo[6.2.1.0(2,7)]undeca-4,9-dienes and 3-thia-tricyclo[6.2.1.0(2,7)]undec-4-enes, respectively. Addition reactions with acrolein, methacrolein, methyl vinyl ketone, acrylic ester, or ethyl propiolate finally yielded ruthenium complexes of 3,4-disubstituted 3,4-dihydro-2H-thiopyrans and 4H-thiopyrans, respectively.

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Section: Discussionsupporting

confidence: 91%

Ruthenium Complexes of Thiocinnamaldehydes: Synthesis, Structure, and [4+2]‐Cycloaddition Reactions

Schenk

Beucke

Burzlaff

et al. 2006

Chemistry A European J

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“…The shortest C2 ؒ ؒ ؒ S distances are in the TSs for reaction (4) while the longest distances are found in TS9nc and TS9xc. We note that these extrema come in pairs corresponding to the different regioisomers: shortest C ؒ ؒ ؒ C in reaction (5), shortest C ؒ ؒ ؒ S in reaction (4); longest C ؒ ؒ ؒ C in reaction (8), longest C ؒ ؒ ؒ S in reaction (9).…”

Section: Geometriesmentioning

confidence: 93%

“…The reaction with methoxyethene proceeds most easily through TS5x, which lies 4.35 kJ mol Ϫ1 below TS4x, while P4x is the most stable product. While reaction (4) shows little endo/ exo selectivity, the exo pathway is favored by 6.32 kJ mol Ϫ1 for reaction (5).…”

Section: Energiesmentioning

confidence: 99%

“…4- 8 For example (see Scheme 2), while the reaction of thioketone 5 with acrylonitrile or acrylamide is in agreement with FMO predictions, 4 the reaction with butyl vinyl ether gives the regioisomer opposite to that predicted by FMO. 5 Their arguments rested on the dominant interaction being between the LUMO of the thioketone and the HOMO of the dienophile.…”

Section: Introductionmentioning

confidence: 99%

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Ab initio study of the Diels–Alder reactions of prop-2-enethial

Bachrach¹,

Jiang²

1998

J. Chem. Soc., Perkin Trans. 2

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“…Synthesis and selected data of other thiochalcones 2 have been previously reported in the literature. [6][7][8]24 3…”

Section: Thiochalcones 2; General Proceduresmentioning

confidence: 99%

First (3+2)-Cycloadditions of Thiochalcones as C=S Dipolarophiles: Efficient Synthesis of 1,3,4-Thiadiazoles via Reactions with Fluorinated Nitrile Imines

Grzelak¹,

Utecht²,

Jasiński³

et al. 2017

Synthesis

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Chemistry of .alpha.,.beta.-unsaturated thione dimers. 2. Reactions of thiochalcones and 2-arylidene-1-thiotetralones with some olefins and the parent ketones of the thiones

Cited by 47 publications

References 1 publication

Ruthenium Complexes of Thiocinnamaldehydes: Synthesis, Structure, and [4+2]‐Cycloaddition Reactions

Ruthenium Complexes of Thiocinnamaldehydes: Synthesis, Structure, and [4+2]‐Cycloaddition Reactions

Ab initio study of the Diels–Alder reactions of prop-2-enethial

First (3+2)-Cycloadditions of Thiochalcones as C=S Dipolarophiles: Efficient Synthesis of 1,3,4-Thiadiazoles via Reactions with Fluorinated Nitrile Imines

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