Diphenylsulfoniummethylid | 40411-90-3

• 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: Diphenylsulfoniummethylid
• 英文别名: Diphenylsulfonium methylide；methylidene(diphenyl)-λ4-sulfane
• CAS: 40411-90-3
• 化学式: C₁₃H₁₂S
• 分子量: 200.304
• InChiKey: KDFWIDQEGGGHAB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  19.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  Diphenylsulfoniummethylid 、 bis(diisopropylamino)phosphenium trifluoromethanesulfonate 以 四氢呋喃 为溶剂， 反应 2.0h， 生成 1-((diphenyl-l4-sulfaneylidene)methyl)-N,N,N',N'-tetraisopropylphosphanediamine
  参考文献：
  名称：

  混合的-bi双氰化物的合成R3P = C = SR2。

  摘要：

  DOI：

  10.1002/anie.200704071
• 作为产物：
  描述：

  diphenylmethylsulfonium tetrafluoroborate 在 sodium hexamethyldisilazane 作用下， 以 四氢呋喃 为溶剂， 生成 Diphenylsulfoniummethylid
  参考文献：
  名称：

  A Diruthenium μ-Carbido Complex That Shows Singlet-Carbene-like Reactivity

  摘要：

  Low-temperature deprotonation of the cationic mu-methylidyne complex [(Cp*Ru)(2)(mu-NPh)(mu-CH)][BF4] (Cp* = eta(5)-C5Me5) with KN(SiMe3)(2) affords a thermally unstable mu-carbido complex [(Cp*Ru)(2)(mu-NPh)(mu-C)] (2), as evidenced by trapping experiments with elemental S or Se and C-13 NMR spectroscopic observation. The reactivity of 2 toward CO2, Ph2S+CH2-, EtOH, and an intramolecular CH bond indicates that the mu-carbido carbon in 2 has an ambiphilic (nucleophilic and electrophilic) nature consistent with the formulation of 2 as the first example of a transition-metal-substituted singlet carbene. DFT study suggests that the Ru substituents in 2 are stronger sigma-donor and weaker pi-donor to the carbene center than amino substituents in N-heterocyclic carbenes.

  DOI：

  10.1021/ja509364d

文献信息

• Protective group tuning in the stereoselective conversion of α-amino aldehydes into aminoalkyl epoxides
  作者：M.T. Reetz、J. Binder

  DOI：10.1016/s0040-4039(01)80584-0

  日期：1989.1

  Sulfonium and arsonium ylides of the type CH2=S(CH3)2 and CH2=As(Ph)3 react with doubly protected α-amino aldehydes derived from amino acids to form aminoalkyl epoxides /, diastereofacial selectivity ranging between 86:14 and 95:5.

  CH 2 = S（CH 3）2和CH 2 = As（Ph）3类型的ulf和砷化物与衍生自氨基酸的双重保护的α-氨基醛反应形成氨基烷基环氧化物/ ，非对映选择性在86:14之间和95：5。
• Parent Cyclopentadienyl Ruthenium(II) Chloride Synthon: Derivatization to CpRu Amido, Imido, and Oxo Complexes
  作者：Shin Takemoto、Hana Ishii、Masahiro Yamaguchi、Akira Teramoto、Masayuki Tsujita、Daiki Ozeki、Hiroyuki Matsuzaka

  DOI：10.1021/acs.organomet.9b00576

  日期：2019.11.11

  dimeric amido complex [CpRu(NHtBu)]2, which is subsequently transformed into the bridging imido complexes [(CpRu)2(μ-NtBu)(μ-CH2)] and [(CpRu)2(μ-NtBu)(μ-CH)]+. The imido methylidyne complex shows enhanced electrophilicity at the methylidyne carbon compared to its bulkier C5Me5 congener and also allows access to a less hindered parent Cp version of the diruthenocarbene ligand in the form of the Ru2Cu

  该配盐[CPRU（η 6 -C 10 ħ 8）] [（CPRU）2（μ-Cl）的3 ]（[ 1 ] [ 2 ]）合成并发现是一种有用的合成子CpRuCl。离子[ 1 ] +和[ 2 ] -干净comproportionate成单体CpRuCl（L）2种复合物用在与供体治疗萘解放配体L例如DMSO，吨BuNH 2，1,5-环，和CO的胺。加合物[CpRuCl（NH 2 t Bu）2]允许访问配位不饱和二聚酰氨基配合物[CPRU（NH吨丁基）] 2，其随后转化成桥接亚氨基配合物[（CPRU）2（μ-N吨卜）（μ-CH 2）]和[ （CPRU）2（μ-N吨卜）（μ-CH）] +。酰亚胺次甲基复杂示出了在次甲基碳增强的亲电性相比，其体积更大Ç 5我5同类并且还允许访问diruthenocarbene配体的较少受阻父的Cp版本中的Ru的形式2的Cuμ 3 -carbido配合物[（ CPRU）2（μ-N吨卜）（μ
• Implication and improvement of stereoselective methylenation of a chiral aldehyde related to total synthesis of the furaquinocins
  作者：Takeshi Saito、Takao Suzuki、Kazuhiro Takeuchi、Takashi Matsumoto、Keisuke Suzuki

  DOI：10.1016/s0040-4039(97)00746-6

  日期：1997.5

  In relation to the total synthesis of the furaquinocins, stereoselective methylenation of chiral aldehyde 5 is described. The diastereoselectivity of epoxides 6a/6b is high when stabilized sulfur ylides are employed. A double stereo-differentiation phenomenon was observed for the aminosulfoxonium ylide 8: the selectivity with (S)-8 was 30:1, while 5:1 with (R)-8.

  关于呋喃喹啉的全合成，描述了手性醛5的立体选择性亚甲基化。当使用稳定的硫磺化物时，环氧化物6a / 6b的非对映选择性很高。对于氨基ulf氧鎓叶立德8观察到双立体分化现象：（S）-8的选择性为30：1，而（R）-8的选择性为5：1 。
• Linear Hydrocarbon Chain Growth from a Molecular Diruthenium Carbide Platform
  作者：Jun Ohata、Akira Teramoto、Hiroaki Fujita、Shin Takemoto、Hiroyuki Matsuzaka

  DOI：10.1021/jacs.1c06586

  日期：2021.10.6

  sequence is initiated by the formation of a μ-η1:η1-C═CH2 ligand from a C + CH2 coupling between the μ-carbido complex [(Cp*Ru)2(η-NPh)(μ-C)] (1; Cp* = η5-C5Me5) and Ph2SCH2. Then, the chain propagates via a general C═CHR + CH2 coupling and subsequent hydrogen-assisted isomerization of the resulting allene ligand μ-η1:η3-H2C═C═CHR to a higher vinylidene homologue μ-η1:η1-C═CH(CH2)R. By repeating this reaction

  通过在金属表面上连续偶联 C 1单元形成线性烃链是费托 (FT) 合成的核心部分。有机金属配合物提供了许多相关单个 C-C 偶联事件的模型，但未能重现以迭代方式将线性 C n烃链转化为其 C n +1同系物的完整链延长序列。在这项工作中，我们展示了线性 C n烃链的逐步增长及其通过连续添加 CH 2转化为 C n +1同系物分子碳化二钌平台上的单元。链增长序列由形成了μ-η的发起1：η 1 -C═CH 2从C + CH配体2的μ-碳化复合物之间的耦合[（CP * Ru）的2（η-NPH）（ μ-C)] ( 1；Cp* = η 5 -C 5 Me 5 )和Ph 2 SCH 2。然后，链通过一般的 C=CHR + CH 2偶联和随后得到的丙二烯配体 μ-n 1 :η 3 -H 2 C =C=CHR 的氢辅助异构化扩展为更高的亚乙烯基同系物 μ-η 1:η 1 -C=CH(CH 2 )R。通过重复该反应序列，最多可逐步合成C
• Diastereoselective conjugate addition and cyclopropanation reactions with nitroalkenes derived from (R)-2,3-isopropylidene glyceraldehyde
  作者：Guido Galley、Jan Hübner、Sven Anklam、Peter G Jones、Michael Pätzel

  DOI：10.1016/0040-4039(96)01374-3

  日期：1996.8

  In the reactions of functionalized organometallics and of cyclopropanation reagents with chiral nitroalkenes 3 the conjugate addition proceeded with modest to high diastereoselectivity depending on the metal and the substituent R. X-ray analyses showed the nitrocyclopropanes 6, formed with high stereoselectivity, to be syn-derivatives.

  在官能化的有机金属和环丙烷化试剂与手性硝基烯烃3的反应中，根据金属和取代基R的不同，共轭加成反应的中等至高非对映选择性。X射线分析表明，具有高立体选择性的硝基环丙烷6是顺式-衍生品。