2-bromo-4-(tert-butyldimethylsiloxy)oct-1-en-3-ol

• 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: 2-bromo-4-(tert-butyldimethylsiloxy)oct-1-en-3-ol
• 英文别名: (3R,4R)-2-bromo-4-[tert-butyl(dimethyl)silyl]oxyoct-1-en-3-ol
• 化学式: C₁₄H₂₉BrO₂Si
• 分子量: 337.373
• InChiKey: VJBMZUUVWSYSGK-OLZOCXBDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.84
• 重原子数：
  18
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-bromo-4-(tert-butyldimethylsiloxy)oct-1-en-3-ol 在 吡啶 、 氟化氢吡啶 作用下， 以 二氯甲烷 为溶剂， 反应 10.0h， 以90%的产率得到2-bromooct-1-en-3,4-diol
  参考文献：
  名称：

  1-Bromo-1-lithioethene:  A Practical Reagent in Organic Synthesis

  摘要：

  A reliable preparative scale synthesis of 1-bromo-1-lithioethene is reported. This reagent undergoes clean 1,2-addition with a range of aldehydes and ketones at -110 degrees C to afford the corresponding 2-bromo-1-alken-3-ols in moderate to excellent yield. Trapping with other electrophiles (acylsilanes, chlorosilanes, tributyltin chloride, iodine) cleanly provides practically useful yields of various 1-substituted 1-bromoethene products. Unexpectedly high diastereoselectivities were observed during the addition of 1-bromo-1-lithioethene to alpha-siloxy aldehydes (typically 10:1, Felkin-Ahn control) and protected ketopyranose and ketofuranose sugars (>= 10:1, addition from the less-hindered face). The title organolithium reagent possesses relatively low basicity at low temperature, and is compatible with a variety of common protecting groups. We believe that these unusual properties of 1-bronio-1-lithioethene may originate from the specific crystalline structure of the reagent in which lithium is coordinatively saturated and thus unavailable for chelation.

  DOI：

  10.1021/jo051125v
• 作为产物：
  描述：

  溴乙烯 、 2-<(tert-Butyldimethylsilyl)oxy>hexanal 在 正丁基锂 、 lithium bromide 、 三甲基氯硅烷 、 水 、 三氟乙酸 作用下， 以 四氢呋喃 、 乙醚 、 正戊烷 、 various solvents 为溶剂， 反应 0.5h， 以49%的产率得到2-bromo-4-(tert-butyldimethylsiloxy)oct-1-en-3-ol
  参考文献：
  名称：

  1-Bromo-1-lithioethene:  A Practical Reagent in Organic Synthesis

  摘要：

  A reliable preparative scale synthesis of 1-bromo-1-lithioethene is reported. This reagent undergoes clean 1,2-addition with a range of aldehydes and ketones at -110 degrees C to afford the corresponding 2-bromo-1-alken-3-ols in moderate to excellent yield. Trapping with other electrophiles (acylsilanes, chlorosilanes, tributyltin chloride, iodine) cleanly provides practically useful yields of various 1-substituted 1-bromoethene products. Unexpectedly high diastereoselectivities were observed during the addition of 1-bromo-1-lithioethene to alpha-siloxy aldehydes (typically 10:1, Felkin-Ahn control) and protected ketopyranose and ketofuranose sugars (>= 10:1, addition from the less-hindered face). The title organolithium reagent possesses relatively low basicity at low temperature, and is compatible with a variety of common protecting groups. We believe that these unusual properties of 1-bronio-1-lithioethene may originate from the specific crystalline structure of the reagent in which lithium is coordinatively saturated and thus unavailable for chelation.

  DOI：

  10.1021/jo051125v

文献信息

• 1-Bromo-1-lithioethene:  A Practical Reagent in Organic Synthesis
  作者：Yehor Y. Novikov、Paul Sampson

  DOI：10.1021/jo051125v

  日期：2005.12.1

  A reliable preparative scale synthesis of 1-bromo-1-lithioethene is reported. This reagent undergoes clean 1,2-addition with a range of aldehydes and ketones at -110 degrees C to afford the corresponding 2-bromo-1-alken-3-ols in moderate to excellent yield. Trapping with other electrophiles (acylsilanes, chlorosilanes, tributyltin chloride, iodine) cleanly provides practically useful yields of various 1-substituted 1-bromoethene products. Unexpectedly high diastereoselectivities were observed during the addition of 1-bromo-1-lithioethene to alpha-siloxy aldehydes (typically 10:1, Felkin-Ahn control) and protected ketopyranose and ketofuranose sugars (>= 10:1, addition from the less-hindered face). The title organolithium reagent possesses relatively low basicity at low temperature, and is compatible with a variety of common protecting groups. We believe that these unusual properties of 1-bronio-1-lithioethene may originate from the specific crystalline structure of the reagent in which lithium is coordinatively saturated and thus unavailable for chelation.