(E)-2-bromo-4-(tert-butyldiphenylsilyloxy)-2-butene | 173044-28-5

• 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: (E)-2-bromo-4-(tert-butyldiphenylsilyloxy)-2-butene
• 英文别名: [(E)-3-bromobut-2-enoxy]-tert-butyl-diphenylsilane
• CAS: 173044-28-5
• 化学式: C₂₀H₂₅BrOSi
• 分子量: 389.407
• InChiKey: VQJUPYZDLWYQRK-BMRADRMJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.86
• 重原子数：
  23
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (E)-2-bromo-4-(tert-butyldiphenylsilyloxy)-2-butene 在 六甲基磷酰三胺 、 叔丁基锂 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 生成 tert-butyl-[(2E,5E,9E)-12-(3,3-dimethyloxiran-2-yl)-3,6,10-trimethyldodeca-2,5,9-trienoxy]-diphenylsilane
  参考文献：
  名称：

  Concise total synthesis of (±)-palominol and (±)-dolabellatrienone via a dianion-accelerated oxy-cope rearrangement

  摘要：

  A short synthesis of (+/-)-palominol (1) and (+/-)-dolabellatrienone (2) starting from farnesol is reported. Noteworthy steps include an intramolecular pinacol coupling to form a 15-membered carbocyclic diol and subsequent dianion-accelerated oxy-Cope rearrangement to form the 11,5-trans-fused ring system of the dolabellanes. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(97)10614-1
• 作为产物：
  描述：

  (E)-3-bromo-2-buten-1-ol 、 叔丁基二苯基氯硅烷 在 咪唑 作用下， 反应 0.5h， 以99%的产率得到(E)-2-bromo-4-(tert-butyldiphenylsilyloxy)-2-butene
  参考文献：
  名称：

  Concise total synthesis of (±)-palominol and (±)-dolabellatrienone via a dianion-accelerated oxy-cope rearrangement

  摘要：

  A short synthesis of (+/-)-palominol (1) and (+/-)-dolabellatrienone (2) starting from farnesol is reported. Noteworthy steps include an intramolecular pinacol coupling to form a 15-membered carbocyclic diol and subsequent dianion-accelerated oxy-Cope rearrangement to form the 11,5-trans-fused ring system of the dolabellanes. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(97)10614-1

文献信息

• Total Synthesis of Dumsin. 1. Retrosynthetic Strategy and the Elaboration of Key Intermediates from (−)-Bornyl Acetate
  作者：Leo A. Paquette、Fang-Tsao Hong

  DOI：10.1021/jo0301346

  日期：2003.9.1

  An intramolecular anionic oxy-Cope rearrangement (44 --> 46) serves as the key step in a synthetic approach to the insect antifeedant dumsin. Initial investigations clarified the manner in which (--)-bornyl acetate may be transformed into the exo-norbornenol 44. Two routes were developed to advance beyond 46. The first involved acetal 51 as a matrix that was expected to allow the elaboration of rings

  分子内阴离子oxy-Cope重排（44-> 46）是昆虫抗饲料dumsin合成方法中的关键步骤。初步研究阐明了乙酸（-）乙酸冰片酯可转化为外降冰片烯醇44的方式。开发了两种方法以超越46。首先涉及乙缩醛51作为基质，预期可精制环D和E。第二个计划将46中的环戊烯环的氧化反应推迟到分子构建的后期。后面的实验构成了协议的基础，该协议导致成功获取以108和114为代表的酮醛。
• Alkali Metal Counterion Control of Enolate Protonation Stereoselectivity
  作者：Yang Hu、Raynauld L. Bishop、Andreas Luxenburger、Shuzhi Dong、Leo A. Paquette

  DOI：10.1021/ol060761s

  日期：2006.6.1

  [reaction: see text] Generation of the lithium salt of the norbornenol shown (M = H) followed by quenching with aqueous NH(4)Cl solution gives predominantly the beta-epimeric ketone 6. Similar production of the potassium alkoxide leads instead to the alpha-epimer (99:1). These results reveal the potential importance of alkali metal counterions as stereocontrol elements.

  [反应：请参阅文本]生成所示的降冰片醇锂盐（M = H），然后用NH（4）Cl水溶液淬灭，主要产生β-表异构体酮6。 alpha-epimer（99：1）。这些结果揭示了碱金属抗衡离子作为立体控制元素的潜在重要性。
• First Enantioselective Total Synthesis of a Naturally Occurring Dolabellane. Revision of Absolute Configuration
  作者：E. J. Corey、Robert S. Kania

  DOI：10.1021/ja9536779

  日期：1996.1.1
• Concise total synthesis of (±)-palominol and (±)-dolabellatrienone via a dianion-accelerated oxy-cope rearrangement
  作者：E.J. Corey、Robert S. Kania

  DOI：10.1016/s0040-4039(97)10614-1

  日期：1998.2

  A short synthesis of (+/-)-palominol (1) and (+/-)-dolabellatrienone (2) starting from farnesol is reported. Noteworthy steps include an intramolecular pinacol coupling to form a 15-membered carbocyclic diol and subsequent dianion-accelerated oxy-Cope rearrangement to form the 11,5-trans-fused ring system of the dolabellanes. (C) 1998 Elsevier Science Ltd. All rights reserved.