threo-C6H5CHDCHDSH | 141664-82-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: threo-C6H5CHDCHDSH
• CAS: 141664-82-6
• 化学式: C₈H₁₀S
• 分子量: 140.218
• InChiKey: ZMRFRBHYXOQLDK-QLUKFHSTSA-N

反应信息

• 作为反应物：
  描述：

  (η5-C5Me5)2Ta(η2-C6H4)H 、 threo-C6H5CHDCHDSH 以 not given 为溶剂， 生成 (η5-C5Me5)2Ta(S)(threo-CHDCHDC6H5) 、 (η5-C5Me5)2Ta(S)(erythro-CHDCHDC6H5)
  参考文献：
  名称：

  Synthesis and characterization of thioaldehyde hydride derivatives of permethyltantalocene. Investigations of their equilibration with thiolates and the stereochemistry of alkyl migrations from sulfur to tantalum

  摘要：

  Permethyltantalocene thioaldehyde hydride complexes, Cp*2Ta(eta-2-S-CHR)H (Cp* = eta-5,-C5Me5; R = H, C6H5, CH2C6H5, CH2CMe3), have been prepared by treating precursors to [Cp*2Ta-R'] (e.g. Cp*2Ta(=C=CH2)H for R' = CH=CH2) with the appropriate thiol RCH2SH. Oxidative addition of the S-H bond leads to the unstable Ta(V) derivatives Cp*2Ta(R')(H)(SCH2R). Reductive elimination of R'H is facile, forming [Cp*2Ta-SCH2R], which subsequently undergoes beta-H elimination to yield the thioaldehyde hydrides Cp*2Ta(eta-2-S-CHR)H. The results of an X-ray structure determination for Cp*2Ta(eta-2-S-CHCH2C6H5) H are summarized. These permethyltantalocene thioaldehyde hydride complexes are shown to be in rapid equilibrium with the corresponding 16-electron thiolate species [Cp*2Ta-SCH2R] through a beta-H migratory insertion/elimination process. When they are heated, the permethyltantalocene thioaldehyde hydride complexes undergo rearrangement to the thermodynamically favored tautomer, the permethyltantalocene sulfido alkyl Cp*2Ta(=S)CH2R. An inverse kinetic deuterium isotope effect observed for Cp*2Ta(eta-2-S-CY2)Y (Y = H, D) (k(H)/k(D) = 0.72 (3) at 138-degrees-C) is indicative of a stepwise process involving fast preequilibrium of Cp*2Ta(eta-2-S-CY2)Y with [Cp*2Ta-SCY3] and rate-determining alpha-CY3 elimination to Cp*2Ta(=S)CY3. Derivatives of the permethyltantalocene phenylthioacetaldehyde hydride have been prepared from the erythro- and threo-phenethyl-d2 mercaptan, C6H5CHDCHDSH, to elucidate the mechanism of alkyl transfer. The migration has been found to proceed with greater-than-or-equal-to 85% retention of stereochemistry at carbon for the migrating phenethyl-d2 group. The sulfido methyl complex Cp*2Ta(=S)CH3 is hydrogenated under forcing conditions to yield methane and Cp*2Ta(=S)H, but this product resists final hydrogenation to Cp*2TaH3 and H2S.

  DOI：

  10.1021/om00042a036