The coordination chemistry of the C:S function. 9. Synthesis of cationic ruthenium thiobenzaldehyde complexes through .beta.-hydride abstraction

Schenk, Wolfdieter A.; Stur, Thomas; Dombrowski, Eberhard

doi:10.1021/ic00031a005

Cited by 32 publications

(23 citation statements)

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“…[23,51] Thus the use of transitionmetal-stabilized thioaldehydes as starting materials provides suitable alternatives for the synthesis of six-membered sulfur heterocycles. In this context it should be mentioned that the cleavage of thioether ligands from halfsandwich ruthenium complexes can be achieved under mild conditions.…”

Section: Discussionmentioning

confidence: 99%

“…[23,24] Here we report the synthesis and reactions of analogous complexes of thiocinnamaldehydes. A preliminary account of this work was included in a recent review.…”

Section: A C H T U N G T R E N N U N G (S=chr)]mentioning

confidence: 99%

“…[23,24] This includes the length of the RuÀ S bond and the orientation of the thioaldehyde ligand with the CÀH bond pointing towards the Cp ring. The unsaturatScheme 1.…”

Section: X-ray Structure Determinations Of [Cprua C H T U N G T R E Nmentioning

confidence: 99%

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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: Discussionmentioning

confidence: 99%

“…[23,24] Here we report the synthesis and reactions of analogous complexes of thiocinnamaldehydes. A preliminary account of this work was included in a recent review.…”

Section: A C H T U N G T R E N N U N G (S=chr)]mentioning

confidence: 99%

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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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“…[3] Mechanistically, this reaction proceeds through a one-elec-nated cysteine moiety. The thioaldehyde intermediate thus formed undergoes nucleophilic attack by the deprotonated tron oxidation of Ru II to Ru III , followed by hydrogen atom abstraction (Equation 1).…”

Section: The Central Step Of Penicillin Biosynthesis Leading To Thementioning

confidence: 99%

“…The thioaldehyde intermediate thus formed undergoes nucleophilic attack by the deprotonated tron oxidation of Ru II to Ru III , followed by hydrogen atom abstraction (Equation 1). [4] amide group of the cysteine [2] (Scheme 1).…”

Section: The Central Step Of Penicillin Biosynthesis Leading To Thementioning

confidence: 99%

Chiral Rhenium Complexes of Functionalized Thioaldehydes

Burzlaff¹,

Schenk²

1999

Eur. J. Inorg. Chem.

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Chiral racemic rhenium thioaldehyde complexes [CpRe(NO)(PPh3)(η2‐S=CHR)]PF6 (2a–g) bearing functionalized aliphatic groups R [R = CH2Ph (a), COOEt (b), CH2COOMe (c), CH2C(O)NHCH2Ph (d), (R)‐CH(NC8H4O2)COOMe (e), (S,S)‐CH(Me)C(O)NC4H7COOMe (f), C4H3O (g)] have been obtained by hydride abstraction from the corresponding thiolate complexes [CpRe(NO)(PPh3)(SCH2R)] (1a–g). With the exception of 2b, only single stereoisomers with like configurations at rhenium and the thioaldehyde carbon atom were obtained. In some cases, the corresponding sulfinate complexes [CpRe(NO)(PPh3)(SO2CH2R)] (3d–f) were formed as by‐products. The analogous toluenesulfinate complex [CpRe(NO)(PPh3){SO2(4‐C6H4CH3)}] (3a) has been prepared from [CpRe(NO)(PPh3)(THF)]BF4 (8), and the structure of 3e has been determined by X‐ray crystallography. The use of phosphorus ligands other than PPh3 was briefly explored with the synthesis of [CpRe(NO)(PR′3)(η2‐S=CHR)]PF6 (5a–d) [R′ = OPh, R = Ph (a), 4‐C6H4Cl (b), R′ = iPr, R = Ph (c), H (d)]. Nucleophilic addition of NaSMe to [CpRe(NO)(PPh3){η2‐S=CH(4‐C6H4OMe)}]PF6 (5e) gave the dithioacetal complex [CpRe(NO)(PPh3){SCH(SMe)(4‐C6H4OMe)}] (9) in high yield and with low diastereoselectivity. Diels–Alder additions of 5a, e with 2,3‐dimethylbutadiene and 2,3‐dimethoxy‐butadiene gave complexes of cyclic thioethers (10a–c). From the relative rates of reaction (5a >> 5e) and the low diastereoselectivity, it was concluded that the cycloadditions as well as the nucleophilic addition proceed via the linkage isomers [CpRe(NO)(PR′3)(η1‐S=CHR)]PF6.

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Synthesis of Chiral Rhenium Complexes Containing Functionalized Thiolate Ligands

Burzlaff

Schenk

1998

Eur. J. Inorg. Chem.

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Chiral racemic rhenium thiolate complexes [CpRe(NO)(PPh3)(SR)] were obtained under either acidic or basic conditions. Thus, when [CpRe(NO)(PPh3)(CH3)] (1) was treated with etheral HBF4 and HSR the thiolate complexes [CpRe(NO)(PPh3)(SR)] [SR = SCH2(2‐furyl) (2), SCH2C(O)OEt (3)] were obtained after chromatographic workup. Ligand exchange reactions between [CpRe(NO)(PPh3)(OC4H8)]BF4 (4) and sodium thiolates yielded analogous complexes with SR = SH (5), SCH2CH2Ph (6), SCH2CH=CH2 (7). SR groups which tolerate strongly alkaline conditions may be introduced by treatment of 4 with HSR in the presence of sodium ethoxide as demonstrated by the high‐yield synthesis of 2 as well as of complexes with SR = SCH2CH2NHAc (8), SCH2CH2C(O)OH (9). A milder synthesis using hydrated sodium carbonate as a base provided 8 and compounds with SR = SCH2CH2C(O)OMe (10), SCH2CH2C(O)NHCH2Ph (11) in high yields. Using similar methods, thiolate complexes of (R)‐N‐acetylcysteine (13), its methyl ester (14), (R)‐N‐phthaloylcysteine (16), and N‐[(S)‐3‐mercapto‐2‐methylpropionyl]‐S‐proline (Captopril) (17) were obtained as diastereomeric pairs. The formation of 13 was preceded by the O‐bonded isomer 12 which slowly rearranges in solution. 13 can be converted under acidic conditions into its methyl (14) or ethyl (15) esters. The diastereomers of 16 were separated by crystallization, and the structure of the (R,R)‐isomer 16a determined.

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The coordination chemistry of the C:S function. 9. Synthesis of cationic ruthenium thiobenzaldehyde complexes through .beta.-hydride abstraction

Cited by 32 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

Chiral Rhenium Complexes of Functionalized Thioaldehydes

Synthesis of Chiral Rhenium Complexes Containing Functionalized Thiolate Ligands

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