(4S)-(-)-2-bromo-4-<(tert-butyldimethylsilyl)oxy>2-cyclopentenone | 137434-22-1

• 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: (4S)-(-)-2-bromo-4-<(tert-butyldimethylsilyl)oxy>2-cyclopentenone
• 英文别名: (4S)-2-Bromo-4-{[tert-butyl(dimethyl)silyl]oxy}-2-cyclopenten-1-one；(4S)-2-bromo-4-[tert-butyl(dimethyl)silyl]oxycyclopent-2-en-1-one
• CAS: 137434-22-1
• 化学式: C₁₁H₁₉BrO₂Si
• 分子量: 291.26
• InChiKey: PIIFULRVBPPSJP-MRVPVSSYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.63
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (4S)-(-)-2-bromo-4-<(tert-butyldimethylsilyl)oxy>2-cyclopentenone 在 sodium tetrahydroborate 、 cerium(III) chloride 、 sodium hydride 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 10.0h， 生成 ((1S,4R)-3-Bromo-4-methoxy-cyclopent-2-enyloxy)-tert-butyl-dimethyl-silane
  参考文献：
  名称：

  Sensitivity of Substitution to the Extent of Self-Immolative Chirality Transfer during Reaction Cascades Originating from Squarate Esters

  摘要：

  Reaction cascades induced by the addition to diisopropyl squarate of at least one cycloalkenyl anion possessing an oxygenated leaving group have been examined for the purpose of evaluating the level of chirality transferred to several new stereogenic centers as the original one is destroyed through beta-elimination. A methoxy group alone necessarily resides too far from the bonding sites involved in conrotatory ring closure of the coiled octatetraene intermediate to have a large impact, viz, greater than 22% ee. The situation is considerably improved if a (tert-butyldimethylsilyl)oxy (OTBS) substituent is positioned nearer to this key helical biasing site. The relative rates of ring closure from the two helices of different pitch now become sufficiently different (>100:1) that mechanistic control by OTBS dominates completely, Finally, an example of overwhelming steric bias is detailed (see 30), showing that electrocyclic control can also be achieved in this manner.

  DOI：

  10.1021/jo962182e
• 作为产物：
  描述：

  2-环戊烯-1-醇,4-[[(1,1-二甲基乙基)二甲基甲硅烷基]氧代]-,(1R,4S)- 在 草酰氯 、 溴 、 二甲基亚砜 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 生成 (4S)-(-)-2-bromo-4-<(tert-butyldimethylsilyl)oxy>2-cyclopentenone
  参考文献：
  名称：

  Synthesis and DNA cleaving abilities of functional neocarzinostatin chromophore analogs. Base discrimination by a simple alcohol

  摘要：

  DOI：

  10.1021/ja00026a022

文献信息

• Bioinspired Total Synthesis of Bipolarolides A and B
  作者：Bo Li、Chuanzhen Tan、Tianhao Ma、Yanxing Jia

  DOI：10.1002/anie.202319306

  日期：2024.3.4

  The bioinspired total synthesis of bipolarolides A and B was achieved by using a lithium-halogen exchange/intermolecular nucleophilic addition to link two enantiomerically enriched fragments, two ring-closing metathesis reactions to assemble the five- and eight-membered rings, and a bioinspired Prins reaction/ether formation cascade cyclization to construct the 5/6/6/6/5 caged skeleton.

  双极内酯 A 和 B 的仿生全合成是通过使用锂卤素交换/分子间亲核加成连接两个对映体富集片段、两个闭环复分解反应来组装五元环和八元环以及仿生 Prins 来实现的。反应/醚形成级联环化构建5/6/6/6/5笼状骨架。
• Sensitivity of Substitution to the Extent of Self-Immolative Chirality Transfer during Reaction Cascades Originating from Squarate Esters
  作者：Leo A. Paquette、Lung Huang Kuo、Ashton T. Hamme、Rüdiger Kreuzholz、Julien Doyon

  DOI：10.1021/jo962182e

  日期：1997.3.1

  Reaction cascades induced by the addition to diisopropyl squarate of at least one cycloalkenyl anion possessing an oxygenated leaving group have been examined for the purpose of evaluating the level of chirality transferred to several new stereogenic centers as the original one is destroyed through beta-elimination. A methoxy group alone necessarily resides too far from the bonding sites involved in conrotatory ring closure of the coiled octatetraene intermediate to have a large impact, viz, greater than 22% ee. The situation is considerably improved if a (tert-butyldimethylsilyl)oxy (OTBS) substituent is positioned nearer to this key helical biasing site. The relative rates of ring closure from the two helices of different pitch now become sufficiently different (>100:1) that mechanistic control by OTBS dominates completely, Finally, an example of overwhelming steric bias is detailed (see 30), showing that electrocyclic control can also be achieved in this manner.
• Synthesis and DNA cleaving abilities of functional neocarzinostatin chromophore analogs. Base discrimination by a simple alcohol
  作者：Masahiro Hirama、Takuya Gomibuchi、Kenshu Fujiwara、Yukio Sugiura、Motonari Uesugi

  DOI：10.1021/ja00026a022

  日期：1991.12