(R,R)-bis[(t-butyl)methylphosphinothioyl]methane | 1192844-56-6

• 分子结构分类: 有机化合物 - 有机磷化合物 - 有机硫代磷化合物
• 英文名称: (R,R)-bis[(t-butyl)methylphosphinothioyl]methane
• 英文别名: bis(t-butylmethylphosphinothioyl)methane；Tert-butyl-[[tert-butyl(methyl)phosphinothioyl]methyl]-methyl-sulfanylidene-lambda5-phosphane；tert-butyl-[[tert-butyl(methyl)phosphinothioyl]methyl]-methyl-sulfanylidene-λ5-phosphane
• CAS: 1192844-56-6
• 化学式: C₁₁H₂₆P₂S₂
• 分子量: 284.407
• InChiKey: SSSOWTRJVZUZKN-STQMWFEESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  64.2
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  (R,R)-bis((boranato(tert-butyl)methyl)phosphino)methane 在 三乙烯二胺 、 sulfur 作用下， 以 甲苯 为溶剂， 反应 16.0h， 生成 (R,R)-bis[(t-butyl)methylphosphinothioyl]methane
  参考文献：
  名称：

  One-ligand Catalytic Asymmetric Deprotonation of a Phosphine Borane: Synthesis of P-Stereogenic Bisphosphine Ligands

  摘要：

  A new protocol for the catalytic asymmetric deprotonation of a phosphine borane using s-BuLi and sub-stoichiometric quantities of chiral diamines is reported. The method involves three sequential additions of s-BuLi, and use of (-)-sparteine or the (+)-sparteine surrogate facilitates access to P-stereogenic phosphines with opposite configuration. The method is exemplified by the catalytic asymmetric synthesis of each enantiomer of precursors to QuinoxP*, trichickenfootphos, and Mini-PHOS.

  DOI：

  10.1021/jo200708e

文献信息

• Synthesis of <i>P</i>-Stereogenic Compounds via Kinetic Deprotonation and Dynamic Thermodynamic Resolution of Phosphine Sulfides: Opposite Sense of Induction Using (−)-Sparteine
  作者：Jonathan J. Gammon、Viktoria H. Gessner、Greg R. Barker、Johan Granander、Adrian C. Whitwood、Carsten Strohmann、Peter O’Brien、Brian Kelly

  DOI：10.1021/ja1060966

  日期：2010.10.6

  at a lithiated carbon atom. The major, thermodynamically preferred diastereomeric (-)-sparteine-complexed lithated phosphine sulfide was investigated by X-ray crystallography and computational methods at the B3LYP/6-31+G(d) level. Through the interconversion of the R(P) and S(P) stereoisomers of the lithiated methylphosphine sulfide, a novel dynamic thermodynamic resolution of a racemic lithiated phosphine

  已经进行了在 (-)-sparteine 存在下使用有机锂碱对二甲基取代的硫化膦进行不对称去质子化的系统研究。在-78°C 下在 Et(2)O 中使用 nBuLi 和 (-)-sparteine 通过动力学控制过程在约 88:12 er 中产生被困加合物，该过程在 B3LYP/6-31+ 上使用计算方法成功预测G(d) 级。通过用前手性亲电试剂（例如新戊醛或 tBuPCl(2)）捕获锂化中间体，可以将这种初始动力学对映选择性提高到 97:3 er。此外，发现锂化甲基膦硫化物的 R(P) 和 S(P) 立体异构体可以在高于 0 °C 的温度下相互转化。这种相互转换是前所未有的，并且不同于在锂化碳原子上立体的有机锂的构型不稳定性。在 B3LYP/6-31+G(d) 水平上通过 X 射线晶体学和计算方法研究了主要的热力学首选非对映体 (-)-sparteine-complexed lithated
• Regioselective Lithiation of Silyl Phosphine Sulfides: Asymmetric Synthesis of <i>P</i>-Stereogenic Compounds
  作者：Jonathan J. Gammon、Peter O’Brien、Brian Kelly

  DOI：10.1021/ol901977p

  日期：2009.11.5

  lithiation of a dimethylphosphine sulfide), a two-step process of regioselective lithiation-trapping and silyl group removal has been used to prepare a range of P-stereogenic compounds, including precursors to diphosphine ligands (e.g., Mini-PHOS). This two-step protocol delivers products with the opposite configuration to that obtained by direct asymmetric lithiation−trapping of a dimethylphosphine sulfide

  从99：1 er的三甲基甲硅烷基取代的磷化氢硫化物（由n -BuLi /（-）-天冬氨酸介导的二甲基膦硫化物的不对称锂化反应生成）开始，分两步进行区域选择性锂化捕获和甲硅烷基去除被用于制备一系列P -stereogenic化合物，包括前体二膦配体（例如，微型-PHOS）。此两步协议可提供与使用n -BuLi /（-）-partaine进行二甲基膦硫化物直接不对称锂化-阱化所获得的产品具有相反配置的产品。
• One-ligand Catalytic Asymmetric Deprotonation of a Phosphine Borane: Synthesis of <i>P</i>-Stereogenic Bisphosphine Ligands
  作者：Johan Granander、Francesco Secci、Steven J. Canipa、Peter O’Brien、Brian Kelly

  DOI：10.1021/jo200708e

  日期：2011.6.3

  A new protocol for the catalytic asymmetric deprotonation of a phosphine borane using s-BuLi and sub-stoichiometric quantities of chiral diamines is reported. The method involves three sequential additions of s-BuLi, and use of (-)-sparteine or the (+)-sparteine surrogate facilitates access to P-stereogenic phosphines with opposite configuration. The method is exemplified by the catalytic asymmetric synthesis of each enantiomer of precursors to QuinoxP*, trichickenfootphos, and Mini-PHOS.