(4S)-4-benzyl-3-[(E,2S,3R)-6-[tert-butyl(dimethyl)silyl]oxy-3-hydroxy-2-methylhex-4-enoyl]-1,3-oxazolidin-2-one | 393795-18-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑烷类
• 英文名称: (4S)-4-benzyl-3-[(E,2S,3R)-6-[tert-butyl(dimethyl)silyl]oxy-3-hydroxy-2-methylhex-4-enoyl]-1,3-oxazolidin-2-one
• CAS: 393795-18-1
• 化学式: C₂₃H₃₅NO₅Si
• 分子量: 433.62
• InChiKey: XXLXICGOQONZBI-NJYVDZPESA-N

物化性质

• 沸点：
  546.3±50.0 °C(Predicted)
• 密度：
  1.104±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.15
• 重原子数：
  30
• 可旋转键数：
  9
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  76.1
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (4S)-4-benzyl-3-[(E,2S,3R)-6-[tert-butyl(dimethyl)silyl]oxy-3-hydroxy-2-methylhex-4-enoyl]-1,3-oxazolidin-2-one 在 咪唑 、 甲醇 、 barium dihydroxide 、 正丁基锂 、 三甲基铝 、 4-甲基苯磺酸吡啶 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 甲苯 为溶剂， 反应 0.5h， 生成 (1E,3E,8E)-(6S,7R)-7,10-Dihydroxy-1-iodo-2,6-dimethyl-deca-1,3,8-trien-5-one
  参考文献：
  名称：

  FR182877 的对映选择性合成提供了其结构的化学合理化并提供了其直接前体的数克数量

  摘要：

  描述了以有效的对映选择性合成有效的微管稳定剂 FR182877 的策略的演变。在这种复杂天然产物的拟议生物发生的指导下，出现了一种解决方案，该解决方案涉及第一个报道的双跨环 Diels-Alder 反应实例，以形成其六环结构的关键元素。这种关键的转变从 19 元大环戊烯创建了一个复杂的五环，以完全非对映控制的方式形成了七个新的立体中心。该方法的效率最终能够制备数克数量的 FR182877 直接前体，以便在需要时转化为相对不稳定的天然产物。应变的反应性，

  DOI：

  10.1021/ja021472b
• 作为产物：
  描述：

  叔丁基二甲基烯丙基硅醚 在 Hoveyda-Grubbs catalyst second generation 作用下， 以 二氯甲烷 为溶剂， 反应 13.0h， 生成 (4S)-4-benzyl-3-[(E,2S,3R)-6-[tert-butyl(dimethyl)silyl]oxy-3-hydroxy-2-methylhex-4-enoyl]-1,3-oxazolidin-2-one
  参考文献：
  名称：

  Sequencing cross-metathesis and non-metathesis reactions to rapidly access building blocks for synthesis

  摘要：

  The olefin cross-metathesis reaction has been sequenced with four common organic transformations in a one- or two-pot manner to rapidly access useful building blocks. Those reactions are: (1) phosphorus-based olefination (e.g.. Wittig and Horner-Wadsworth-Emmons); (2) hydride reduction; (3) Evans propionate aldol reaction; (4) Brown allyl- and Roush crotyl-boration. The products of these reactions include stereodefined 2,4-dienoates, trans allylic alcohols, syn-propionate aldols, and chiral non-racemic homoallylic alcohols, respectively. Many of these intermediates have been carried further to natural products, demonstrating the utility of the methodology. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2011.01.080

文献信息

• Intramolecular Allenolate Acylations in Studies toward a Synthesis of FR182877
  作者：Christopher D. Vanderwal、David A. Vosburg、Erik J. Sorensen

  DOI：10.1021/ol016994v

  日期：2001.12.1

  [GRAPHICS]During our efforts to synthesize the cytotoxic natural product FR182877, we discovered intramolecular reductive acylations that offer a stereocontrolled alternative to the classical Knoevenagel condensation for the formation of alpha -alkylidene beta -keto-delta -lactones. Other progress toward a synthesis of FR182877 includes a pi -allyl Stille coupling and a bromo Horner-Wadsworth-Emmons reaction that forms a 12-membered ring. Structural relationships among FR182877, hexacyclinic acid, macquarimicin A, and cochleamycin A are also discussed.
• Sequencing cross-metathesis and non-metathesis reactions to rapidly access building blocks for synthesis
  作者：Gopal Sirasani、Tapas Paul、Rodrigo B. Andrade

  DOI：10.1016/j.tet.2011.01.080

  日期：2011.3

  The olefin cross-metathesis reaction has been sequenced with four common organic transformations in a one- or two-pot manner to rapidly access useful building blocks. Those reactions are: (1) phosphorus-based olefination (e.g.. Wittig and Horner-Wadsworth-Emmons); (2) hydride reduction; (3) Evans propionate aldol reaction; (4) Brown allyl- and Roush crotyl-boration. The products of these reactions include stereodefined 2,4-dienoates, trans allylic alcohols, syn-propionate aldols, and chiral non-racemic homoallylic alcohols, respectively. Many of these intermediates have been carried further to natural products, demonstrating the utility of the methodology. (C) 2011 Elsevier Ltd. All rights reserved.
• An Enantioselective Synthesis of FR182877 Provides a Chemical Rationalization of Its Structure and Affords Multigram Quantities of Its Direct Precursor
  作者：Christopher D. Vanderwal、David A. Vosburg、Sven Weiler、Erik J. Sorensen

  DOI：10.1021/ja021472b

  日期：2003.5.1

  the potent microtubule-stabilizing agent FR182877 is described. Guided by a proposed biogenesis of this complex natural product, a solution emerged that involved the first reported example of a double transannular Diels-Alder reaction to fashion the key elements of its hexacyclic structure. This pivotal transformation creates a complex pentacycle from a 19-membered macrocyclic pentaene, forming seven

  描述了以有效的对映选择性合成有效的微管稳定剂 FR182877 的策略的演变。在这种复杂天然产物的拟议生物发生的指导下，出现了一种解决方案，该解决方案涉及第一个报道的双跨环 Diels-Alder 反应实例，以形成其六环结构的关键元素。这种关键的转变从 19 元大环戊烯创建了一个复杂的五环，以完全非对映控制的方式形成了七个新的立体中心。该方法的效率最终能够制备数克数量的 FR182877 直接前体，以便在需要时转化为相对不稳定的天然产物。应变的反应性，