(1S,6R,8R)-8-Vinyl-2,9,10-trioxa-1-phospha-bicyclo[4.3.1]dec-4-ene 1-oxide | 887143-81-9

• 分子结构分类: 有机化合物 - 有机酸及其衍生物
• 英文名称: (1S,6R,8R)-8-Vinyl-2,9,10-trioxa-1-phospha-bicyclo[4.3.1]dec-4-ene 1-oxide
• CAS: 887143-81-9
• 化学式: C₈H₁₁O₄P
• 分子量: 202.147
• InChiKey: HEFHKSYPUAMSGC-UVPNAGLESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.04
• 重原子数：
  13.0
• 可旋转键数：
  1.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  44.76
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  (1S,6R,8R)-8-Vinyl-2,9,10-trioxa-1-phospha-bicyclo[4.3.1]dec-4-ene 1-oxide 在 Hoveyda-Grubbs catalyst second generation lithium aluminium tetrahydride 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 生成 (2Z,4R,6R,7E,9R)-10-(benzyloxy)deca-2,7-diene-1,4,6,9-tetraol
  参考文献：
  名称：

  Temporary Phosphate Tethers:  A Metathesis Strategy to Differentiated Polyol Subunits

  摘要：

  Studies probing reactivity and selectivity of cross metathesis (CM) with an exocyclic olefin in a P-chiral bicyclo[4.3.1]phosphate triester are described. Studies have revealed a Type III CM reactivity pattern for the exocyclic olefin within this phosphate triester. This versatile method allows for simple, selective manipulation of a P-chiral building block en route to advanced polyol subunits.

  DOI：

  10.1021/ol0602809
• 作为产物：
  描述：

  (4R,6R)-2-chloro-4,6-bis(ethenyl)-1,3,2lambda5-dioxaphosphinane 2-oxide 在 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) 作用下， 以 四氢呋喃 为溶剂， 生成 (1S,6R,8R)-8-Vinyl-2,9,10-trioxa-1-phospha-bicyclo[4.3.1]dec-4-ene 1-oxide
  参考文献：
  名称：

  Temporary Phosphate Tethers:  A Metathesis Strategy to Differentiated Polyol Subunits

  摘要：

  Studies probing reactivity and selectivity of cross metathesis (CM) with an exocyclic olefin in a P-chiral bicyclo[4.3.1]phosphate triester are described. Studies have revealed a Type III CM reactivity pattern for the exocyclic olefin within this phosphate triester. This versatile method allows for simple, selective manipulation of a P-chiral building block en route to advanced polyol subunits.

  DOI：

  10.1021/ol0602809

文献信息

• Synthesis of the C9–C25 Subunit of Spirastrellolide B
  作者：Soma Maitra、Mahipal Bodugam、Salim Javed、Paul R. Hanson

  DOI：10.1021/acs.orglett.6b01248

  日期：2016.7.1

  synthetic features included the union of the two key fragments 5 and 6 via a Suzuki–Miyaura coupling reaction and a late-stage, one-pot sequential deprotection/cascade Achmatowicz rearrangement–spiroketalization to install the key spirocyclic intermediate present in the C9–C25 fragment of spirastrellolide B. The synthesis of the C9–C16 fragment 6 was accomplished via a phosphate tether mediated ring-closing

  据报道，海洋天然产物螺旋藻内酯B的C9–C25亚基的合成。关键的合成特征包括通过铃木-Miyaura偶联反应将两个关键片段5和6结合，以及后期的一锅顺序脱保护/级联Achmatowicz重排-螺缩酮化反应，以安装存在于C9-中的关键螺环中间体螺旋藻内酯B的C25片段。C9–C16片段6的合成是通过磷酸酯系链介导的闭环复分解（RCM），随后的硼氢化-氧化方法以及随后的其他立体选择性转化来实现的。利用Lindlar / NaBH 4将螺环中间体进一步官能化还原方案，以提供C9–C25亚基3。
• Phosphate Tether-Mediated Approach to the Formal Total Synthesis of (−)-Salicylihalamides A and B
  作者：Rambabu Chegondi、Mary M. L. Tan、Paul R. Hanson

  DOI：10.1021/jo200337v

  日期：2011.5.20

  A concise formal synthesis of the cytotoxic macrolides (−)-salicylihalamides A and B is reported. Key features of the synthetic strategy include a chemoselective hydroboration, highly regio- and diastereoselective methyl cuprate addition, Pd-catalyzed formate reduction, and an E-selective ring-closing metathesis to construct the 12-membered macrocycle subunit. Overall, two routes have been developed

  报告了细胞毒性大环内酯 (−)-水杨基卤酰胺 A 和 B 的简明正式合成。该合成策略的关键特征包括化学选择性硼氢化、高度区域和非对映选择性铜酸甲酯加成、Pd 催化的甲酸还原以及 E 选择性闭环复分解以构建 12 元大环亚基。总体而言，已经从易于制备的双环磷酸酯（4 个步骤）开发了两条路线，一条是 13 步路线，另一条是依赖于关键二醇的区域选择性酯化的更有效的 9 步顺序。
• A Multifaceted Phosphate Tether:  Application to the C1−C14 Subunit of Dolabelides A−D
  作者：Joshua D. Waetzig、Paul R. Hanson

  DOI：10.1021/ol7025944

  日期：2008.1.1

  A phosphate tether approach to the C1-14 subunit of dolabelide is described. The phosphate tether serves a multifaceted role mediating several processes, including (i) diastereotopic differentiation via RCM, (ii) selective CM by imparting Type III behavior to the exocyclic olefin, (iii) regioselective hydrogenation, and (iv) regioselective Pd(0)-catalyzed reductive opening of the bicyclic phosphate. Overall, this strategy uses orthogonal protecting- and leaving-group properties innate to phosphate esters to rapidly assembly the titled subunit.
• Total Synthesis of Dolabelide C: A Phosphate-Mediated Approach
  作者：Paul R. Hanson、Rambabu Chegondi、John Nguyen、Christopher D. Thomas、Joshua D. Waetzig、Alan Whitehead

  DOI：10.1021/jo2003506

  日期：2011.6.3

  The first synthesis of dolabelide C (1), a cytotoxic marine macrolide, is reported utilizing a phosphate tether-mediated approach. Bicyclic phosphates (S,S,S-p)-5 and (R,R,R-p)-5 serve as the central building blocks for the construction of two major 1,3-anti-diol subunits in 1 through selective cleavage pathways, regioselective olefin reduction, and cross-metathesis. Overall, phosphate-mediated processes provided copious amounts of both major subunits allowing for a detailed RCM macrocyclization study to the 24-membered macrolactone 1.