phenyl (2R)-3-(tert-butyldiphenylsilyl)oxy-2-methylpropyl sulfide | 189223-93-6

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: phenyl (2R)-3-(tert-butyldiphenylsilyl)oxy-2-methylpropyl sulfide
• 英文别名: tert-butyl-[(2R)-2-methyl-3-phenylsulfanylpropoxy]-diphenylsilane
• CAS: 189223-93-6
• 化学式: C₂₆H₃₂OSSi
• 分子量: 420.691
• InChiKey: NEHMMOHJHLZIPO-JOCHJYFZSA-N

物化性质

• 沸点：
  488.2±37.0 °C(Predicted)
• 密度：
  1.06±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.99
• 重原子数：
  29
• 可旋转键数：
  9
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  34.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  phenyl (2R)-3-(tert-butyldiphenylsilyl)oxy-2-methylpropyl sulfide 在 Oxone 、 四丁基氟化铵 作用下， 以 四氢呋喃 、 甲醇 、 水 为溶剂， 反应 27.0h， 生成 (2R)-2-methyl-3-(phenylsulfonyl)propan-1-ol
  参考文献：
  名称：

  Total Synthesis of Polycavernoside A, A Lethal Toxin of the Red Alga Polycavernosa tsudai

  摘要：

  Two approaches to the synthesis of the aglycon 120 of polycavernoside A (1) were developed, only one of which was completed. The successful "second-generation" route assembled the aglycon seco acids 102 and 106 via Nozaki-Hiyama-Kishi coupling of aldehyde 70, prepared from methyl (S)3-hydroxy-2-methylpropionate (72) and (S)-pantolactone (73), with vinyl bromide 71. The latter was obtained from a sequence which commenced from the silyl ether 24 of 3-hydroxypropionaldehyde and entailed cyclization of (Z)-zeta -hydroxy-alpha,beta-unsaturated ester 82. Regioselective Yamaguchi lactonization of trihydroxycarboxylic acids 102 and 106 and subsequent functional-group adjustments led to macrolactone 120, to which the fucopyranosylxylopyranoside moiety was attached. Stille coupling of the glycosidated aglycon 128 with dienylstannane 129 furnished polycavernoside A in a synthesis for which the longest linear sequence was 25 steps. The overall yield to lactone 120 was 4.7%.

  DOI：

  10.1021/jo0503862
• 作为产物：
  描述：

  (S)-3-(tert-butyldiphenylsilyloxy)-2-methylpropyl acetate 在 咪唑 、 碘 、 potassium carbonate 、 三苯基膦 作用下， 以 甲醇 、 乙醚 、 乙醇 、 乙腈 为溶剂， 反应 52.0h， 生成 phenyl (2R)-3-(tert-butyldiphenylsilyl)oxy-2-methylpropyl sulfide
  参考文献：
  名称：

  芸苔素内酯的正式合成

  摘要：

  酶催化的C 2v形四醇-硫化物中羟基的分化，结合E-立体收敛的Ramberg-Bäcklund工艺，可以制备纯净的（2 S）-2,3-二甲基-1-碘丁烷加上3,5-环戊烯-20-硫代甲醇衍生物，以提供标题植物激素的有效前体。

  DOI：

  10.1016/s0040-4039(97)00474-7

文献信息

• Total Synthesis of Polycavernoside A, A Lethal Toxin of the Red Alga <i>Polycavernosa </i><i>t</i><i>sudai</i>
  作者：Paul R. Blakemore、Cindy C. Browder、Jian Hong、Christopher M. Lincoln、Pavel A. Nagornyy、Lonnie A. Robarge、Duncan J. Wardrop、James D. White

  DOI：10.1021/jo0503862

  日期：2005.7.1

  Two approaches to the synthesis of the aglycon 120 of polycavernoside A (1) were developed, only one of which was completed. The successful "second-generation" route assembled the aglycon seco acids 102 and 106 via Nozaki-Hiyama-Kishi coupling of aldehyde 70, prepared from methyl (S)3-hydroxy-2-methylpropionate (72) and (S)-pantolactone (73), with vinyl bromide 71. The latter was obtained from a sequence which commenced from the silyl ether 24 of 3-hydroxypropionaldehyde and entailed cyclization of (Z)-zeta -hydroxy-alpha,beta-unsaturated ester 82. Regioselective Yamaguchi lactonization of trihydroxycarboxylic acids 102 and 106 and subsequent functional-group adjustments led to macrolactone 120, to which the fucopyranosylxylopyranoside moiety was attached. Stille coupling of the glycosidated aglycon 128 with dienylstannane 129 furnished polycavernoside A in a synthesis for which the longest linear sequence was 25 steps. The overall yield to lactone 120 was 4.7%.
• A formal synthesis of brassinolide
  作者：T. Schmittberger、D. Uguen

  DOI：10.1016/s0040-4039(97)00474-7

  日期：1997.4

  Enzyme-catalysed differentiation of hydroxy groups in a C2v-shaped tetraol-sulfide, combined with a E-stereoconvergent Ramberg-Bäcklund process, allowed to prepare pure (2S)-2,3-dimethyl-1-iodobutane, which could be coupled with a 3,5-cyclopregnane-20-thiomethanol derivative so as to give an efficient precursor of the title vegetal hormone.

  酶催化的C 2v形四醇-硫化物中羟基的分化，结合E-立体收敛的Ramberg-Bäcklund工艺，可以制备纯净的（2 S）-2,3-二甲基-1-碘丁烷加上3,5-环戊烯-20-硫代甲醇衍生物，以提供标题植物激素的有效前体。