Access to central carbon chirality through cycloplatination of 1-(2-pyridinylthio)propanone by cis-[PtCl2(S-SOMe(p-tolyl))].: The crystal structure of (SsSc)-[Pt{py{SCHC(O)Me}-2}Cl(SOMe(p-tolyl))]

被引：28

作者：

Ryabov, AD ^{[1
]}

Panyashkina, IM

Polyakov, VA

Fischer, A

机构：

[1] Moscow MV Lomonosov State Univ, Dept Chem, Moscow 119899, Russia

[2] DI Mendeleev Moscow Acad Chem Technol, Moscow 125820, Russia

[3] Royal Inst Technol, Dept Chem, S-10044 Stockholm, Sweden

来源：

ORGANOMETALLICS | 2002年 / 21卷 / 08期

关键词：

D O I：

10.1021/om0109399

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Cycloplatination of the prochiral sp(3)C-H bond of 1-(2-pyridinylthio)propanone (py(SCH2C(O)Me)(-2), 1a) by cis-[PtCl2(SOMe2)] in dry ethanol affords [Pt(py(SCHC(O)Me)-2)Cl(SOMe2)] (3a) in 77% isolated yield without any side product. The same reaction using the chiral complex cis-[PtCl2(S-SOMe(p-tolyl))] (the absolute configuration of sulfur is indicated for the coordinated ligand) leads to two cycloplatinated diastereoisomers, 4a (SsRc) and 4b (SsSc), in 12.9 and 33.7% yield, respectively (de 44.6%). Their absolute configuration was deduced from the analysis of the H-1 NMR spectra and confirmed by an X-ray structural investigation of 4b. Diastereomer 4b was shown to react with PPh3 to give the enantiomer [Pt(py(SCHC(O)Me)-2)Cl(PPh3)] with the central carbon chirality only. Rather surprisingly, attempted cycloplatination Of py(SCH2C(O)Ph)-2 (1b) by cis-[PtCl2(SOMe2)] affords the cycloplatinated complex [Pt(pyf(SCHC(O)Ph)-2)Cl(SOMe2)] (3b) in a miserable yield.

引用

页码：1633 / 1636

页数：4

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