ethyl N-[(1S,2S,6S)-6-hydroxy-2-[hydroxy(dimethyl)silyl]cyclohex-3-en-1-yl]carbamate | 188981-72-8

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: ethyl N-[(1S,2S,6S)-6-hydroxy-2-[hydroxy(dimethyl)silyl]cyclohex-3-en-1-yl]carbamate
• CAS: 188981-72-8
• 化学式: C₁₁H₂₁NO₄Si
• 分子量: 259.378
• InChiKey: VIXOAWOEHHNANY-GUBZILKMSA-N

物化性质

• 沸点：
  400.8±45.0 °C(Predicted)
• 密度：
  1.13±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.99
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  78.8
• 氢给体数：
  3
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  ethyl N-[(1S,2S,6S)-6-hydroxy-2-[hydroxy(dimethyl)silyl]cyclohex-3-en-1-yl]carbamate 在 potassium fluoride 、 双氧水 、 碘 、 碳酸氢钠 、 potassium hydrogencarbonate 、 对甲苯磺酸 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 N,N-二甲基甲酰胺 、 乙腈 、 苯 为溶剂， 反应 25.0h， 生成 (3aS,5aS,8aS,8bR)-7,7-Dimethyl-2-oxo-3-(toluene-4-sulfonyl)-2,3,3a,5a,8a,8b-hexahydro-benzo[1,2-d;3,4-d']bisoxazole-8-carboxylic acid ethyl ester
  参考文献：
  名称：

  二烯基硅烷的不对称氨基羟基化。氨基环糖醇的有效途径

  摘要：

  甲硅烷基2,5-环己二烯的无尖锐的不对称氨基羟基化反应发生，具有完全的区域和非对映异构控制。还观察到高达68％ee的对映选择性。描述了该方法在氨基-环醇的相关实例的合成中的应用。

  DOI：

  10.1016/s0040-4039(97)00079-8
• 作为产物：
  描述：

  氨基甲酸乙酯 、 Cyclohexa-2,5-dienyl-dimethyl-silanol 在 sodium hydroxide 、 (8a,9R,8′′′a,9′′′R)-9,9′-[(2,5-diphenylpyrimidine-4,6-diyl)bis(oxy)]bis(6′-methoxy-10,11-dihydrocinchonan) 、 potassium dioxotetrahydroxoosmate(VI) 、 次氯酸叔丁酯 作用下， 以 丙醇 、 水 为溶剂， 反应 1.5h， 生成 ethyl N-[(1S,2S,6S)-6-hydroxy-2-[hydroxy(dimethyl)silyl]cyclohex-3-en-1-yl]carbamate
  参考文献：
  名称：

  Desymmetrization of Cyclohexadienylsilanes. Regio-, Diastereo-, and Enantioselective Access to Sugar Mimics

  摘要：

  Desymmetrization of cyclohexadienylsilanes available from Birch reduction of the corresponding arylsilanes is efficiently carried out using Sharpless asymmetric dihydroxylation and aminohydroxylation. Complete diastereocontrol and reasonable enantiocontrol have been attained during the preparation of the desired diols. An excellent regiocontrol has also been observed during aminohydroxylation of dienylsilanol 6b. The resulting diol 8 and hydroxycarbamate 27 have then been elaborated further, offering a straightforward access to various types of cyclitols, aminocyclitols, carbasugars, as well as the antibiotic palitantine 4. The complete functionalization of the original arylsilanes 5 is thus typically achieved in fewer than eight steps with high stereoselectivities and excellent overall yield.

  DOI：

  10.1021/jo991225z

文献信息

• Landais, Yannick, Chimia, 1998, vol. 52, # 3, p. 104 - 111
  作者：Landais, Yannick

  DOI：——

  日期：——
• Desymmetrization of Cyclohexadienylsilanes. Regio-, Diastereo-, and Enantioselective Access to Sugar Mimics
  作者：Rémy Angelaud、Odile Babot、Trevor Charvat、Yannick Landais

  DOI：10.1021/jo991225z

  日期：1999.12.1

  Desymmetrization of cyclohexadienylsilanes available from Birch reduction of the corresponding arylsilanes is efficiently carried out using Sharpless asymmetric dihydroxylation and aminohydroxylation. Complete diastereocontrol and reasonable enantiocontrol have been attained during the preparation of the desired diols. An excellent regiocontrol has also been observed during aminohydroxylation of dienylsilanol 6b. The resulting diol 8 and hydroxycarbamate 27 have then been elaborated further, offering a straightforward access to various types of cyclitols, aminocyclitols, carbasugars, as well as the antibiotic palitantine 4. The complete functionalization of the original arylsilanes 5 is thus typically achieved in fewer than eight steps with high stereoselectivities and excellent overall yield.
• Asymmetric amino-hydroxylation of dienylsilanes. An efficient route to amino-cyclitols
  作者：Rémy Angelaud、Yannick Landais、Kurt Schenk

  DOI：10.1016/s0040-4039(97)00079-8

  日期：1997.2

  Sharpless asymmetric amino-hydroxylation of a silyl-2,5-cyclohexadiene occurs with complete regio- and diastereocontrol. An enantioselectivity of up to 68% e.e. was also observed. An application of the methodology to the synthesis of relevant examples of amino-cyclitols is described.

  甲硅烷基2,5-环己二烯的无尖锐的不对称氨基羟基化反应发生，具有完全的区域和非对映异构控制。还观察到高达68％ee的对映选择性。描述了该方法在氨基-环醇的相关实例的合成中的应用。