(4R,6R)-2-chloro-4,6-bis(ethenyl)-1,3,2lambda5-dioxaphosphinane 2-oxide | 887343-97-7

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磷酸及其衍生物
• 英文名称: (4R,6R)-2-chloro-4,6-bis(ethenyl)-1,3,2lambda5-dioxaphosphinane 2-oxide
• 英文别名: (4R,6R)-2-chloro-4,6-bis(ethenyl)-1,3,2λ5-dioxaphosphinane 2-oxide
• CAS: 887343-97-7
• 化学式: C₇H₁₀ClO₃P
• 分子量: 208.581
• InChiKey: AIMRIXKDIOEJTI-BQBZGAKWSA-N

物化性质

• 沸点：
  193.8±40.0 °C(Predicted)
• 密度：
  1.24±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  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
• 作为产物：
  描述：

  (3R,5R)-hepta-1,6-diene-3,5-diol 在 4-二甲氨基吡啶 、 三乙胺 、 三氯氧磷 作用下， 以 二氯甲烷 为溶剂， 反应 0.42h， 以70%的产率得到(4R,6R)-2-chloro-4,6-bis(ethenyl)-1,3,2lambda5-dioxaphosphinane 2-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

• Phosphate Tether-Mediated Ring-Closing Metathesis for the Generation of <i>P</i>-Stereogenic, <i>Z</i>-Configured Bicyclo[7.3.1]- and Bicyclo[8.3.1]phosphates
  作者：Jana L. Markley、Soma Maitra、Paul R. Hanson

  DOI：10.1021/acs.joc.5b02473

  日期：2016.2.5

  A phosphate tether-mediated ring-closing metathesis (RCM) study to the synthesis of Z-configured, P-stereogenic bicyclo[7.3.1]- and bicyclo[8.3.1]phosphates is reported. Investigations suggest that C3-substitution, olefin substitution, and proximity of the forming olefin to the bridgehead carbon of the bicyclic affect the efficiency and stereochemical outcome of the RCM event. This study demonstrates

  报道了磷酸酯系链介导的闭环复分解（RCM）研究合成Z-构型，P-立体异构的双环[7.3.1]-和双环[8.3.1]磷酸酯。研究表明，C3的取代，烯烃的取代以及形成的烯烃与双环桥头碳的接近度会影响RCM事件的效率和立体化学结果。这项研究证明了磷酸酯系链介导的C 2对称，含1,3-抗二醇的二烯的不对称化在具有潜在的合成和生物学用途的大环磷酸酯的产生中的效用。
• Phosphate-Tether-Mediated Ring-Closing Metathesis for the Preparation of Complex 1,3-<i>anti</i>-Diol-Containing Subunits
  作者：Rambabu Chegondi、Soma Maitra、Jana L. Markley、Paul R. Hanson

  DOI：10.1002/chem.201300913

  日期：2013.6.17

  phosphate‐tether‐mediated ring‐closing metathesis reactions, which highlight the importance of product ring size and substrate stereochemical compatibility, as well as complexity, is reported. Studies focus primarily on the formation of bicyclo[n.3.1]phosphates, involving the coupling of C2‐symmetric dienediol subunits with a variety of simple, as well as complex, alcohol partners.

  报告了一系列非对映选择性、磷酸盐系链介导的闭环复分解反应的例子，它们强调了产物环大小和底物立体化学相容性以及复杂性的重要性。研究主要集中在双环 [ n .3.1] 磷酸酯的形成上，涉及C 2对称二烯二醇亚基与各种简单和复杂的醇伙伴的偶联。
• Phosphate tether-mediated ring-closing metathesis for the generation of medium to large, P-stereogenic bicyclo[n.3.1]phosphates
  作者：Soma Maitra、Jana L. Markley、Rambabu Chegondi、Paul R. Hanson

  DOI：10.1016/j.tet.2015.06.016

  日期：2015.9

  A phosphate tether-mediated ring-closing metathesis study towards the synthesis of P-stereogenic bicyclo[6.3.1]-, bicyclo[7.3.1]-, and bicyclo[8.3.1]phosphates is reported. This study demonstrates expanded utility of phosphate tether-mediated desymmetrization of C2-symmetric, 1,3-anti-diol dienes in generating complex medium to large, P-stereogenic bicyclo[n.3.1]phosphates.

  报道了磷酸酯系链介导的闭环复分解研究，其合成P-立体异构双环[6.3.1]-，双环[7.3.1]-和双环[8.3.1]磷酸。这项研究表明，磷酸酯系链介导的C 2对称的1,3-抗二醇二烯脱对称作用在产生大到P立体异构双环[n.3.1]磷酸盐的复杂介质中具有扩展的效用。
• Total Synthesis of Sanctolide A and Formal Synthesis of (2<i>S</i>)-Sanctolide A
  作者：Gihan C. Dissanayake、Cornelius N. Ndi、Jana L. Markley、James B. Martinez、Paul R. Hanson

  DOI：10.1021/acs.joc.2c01922

  日期：2023.1.20

  sequential protocols for the total synthesis of the polyketide nonribosomal peptide macrolide, sanctolide A, and the formal synthesis of the (2S)-epimer of sanctolide A are reported. In this work, a phosphate tether-mediated one-pot sequential ring-closing metathesis/cross metathesis/substrate-controlled “H2”/tether removal approach was developed to accomplish the total synthesis of the natural product sanctolide

  报道了两种合成策略，采用磷酸系链介导的一锅顺序方案来全合成聚酮化合物非核糖体肽大环内酯、santolide A，以及正式合成 sainttolide A 的 (2 S )-差向异构体。本工作开发了一种磷酸链介导的一锅顺序闭环复分解/交叉复分解/底物控制的“H 2 ”/链去除方法来完成天然产物santolide A的全合成。
• Temporary Phosphate Tethers:  A Metathesis Strategy to Differentiated Polyol Subunits
  作者：Joshua D. Waetzig、Paul R. Hanson

  DOI：10.1021/ol0602809

  日期：2006.4.1

  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.