(4S,6S)-2-chloro-4,6-bis(ethenyl)-2-oxido-1,3,2-dioxaphosphinan-2-ium | 862973-36-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧杂环化合物
• 英文名称: (4S,6S)-2-chloro-4,6-bis(ethenyl)-2-oxido-1,3,2-dioxaphosphinan-2-ium
• CAS: 862973-36-2
• 化学式: C₇H₁₀ClO₃P
• 分子量: 208.581
• InChiKey: AIMRIXKDIOEJTI-RNFRBKRXSA-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：
  41.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (4S,6S)-2-chloro-4,6-bis(ethenyl)-2-oxido-1,3,2-dioxaphosphinan-2-ium 在 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) 2,6-二甲基吡啶 、 9-borabicyclo[3.3.1]nonane dimer 、 正丁基锂 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 25.75h， 生成 (6S,8R)-8-[2-(tert-Butyl-diphenyl-silanyloxy)-ethyl]-2,9,10-trioxa-1-phospha-bicyclo[4.3.1]dec-4-ene 1-oxide
  参考文献：
  名称：

  Multivalent Activation in Temporary Phosphate Tethers:  A New Tether for Small Molecule Synthesis

  摘要：

  A new tether for small molecule synthesis is reported. This functionally active tether mediates the desymmetrization of a pseudo-C-2-symmetric tris-allylic phosphate triester to generate a P-chiral bicyclo[4.3.1]phosphate containing ample steric and stereoelectronic differentiation for investigating chemo-, regio-, and stereoselective transformations. Overall, the method reported herein demonstrates a fundamentally new role of phosphates in synthesis and provides differentiated polyol building blocks for use in natural product synthesis.

  DOI：

  10.1021/ol0512886
• 作为产物：
  描述：

  (3S,5S)-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90%的产率得到(4S,6S)-2-chloro-4,6-bis(ethenyl)-2-oxido-1,3,2-dioxaphosphinan-2-ium
  参考文献：
  名称：

  Multivalent Activation in Temporary Phosphate Tethers:  A New Tether for Small Molecule Synthesis

  摘要：

  A new tether for small molecule synthesis is reported. This functionally active tether mediates the desymmetrization of a pseudo-C-2-symmetric tris-allylic phosphate triester to generate a P-chiral bicyclo[4.3.1]phosphate containing ample steric and stereoelectronic differentiation for investigating chemo-, regio-, and stereoselective transformations. Overall, the method reported herein demonstrates a fundamentally new role of phosphates in synthesis and provides differentiated polyol building blocks for use in natural product synthesis.

  DOI：

  10.1021/ol0512886

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。
• A modular phosphate tether-mediated divergent strategy to complex polyols
  作者：Paul R Hanson、Susanthi Jayasinghe、Soma Maitra、Cornelius N Ndi、Rambabu Chegondi

  DOI：10.3762/bjoc.10.242

  日期：——

  An efficient and divergent synthesis of polyol subunits utilizing a phosphate tether-mediated, one-pot, sequential RCM/CM/reduction process is reported. A modular, 3-component coupling strategy has been developed, in which, simple “order of addition” of a pair of olefinic-alcohol components to a pseudo-C₂-symmetric phosphoryl chloride, coupled with the RCM/CM/reduction protocol, yields five polyol fragments. Each of the product polyols bears a central 1,3-anti-diol subunit with differential olefinic geometries at the periphery.

  报道了一种利用磷酸酯链介导的一锅法、顺序RCM/CM/还原过程的高效、分散的聚醇亚单位合成方法。开发了一种模块化的3组分偶联策略，其中，将一对烯烃-醇组分简单地按顺序加入拟C2对称性磷酰氯中，并结合RCM/CM/还原协议，可以产生五个聚醇片段。每个产物聚醇都带有一个中心的1,3-反式-二醇亚基，在其周围具有不同的烯烃几何构型。
• Multivalent Activation in Temporary Phosphate Tethers:  A New Tether for Small Molecule Synthesis
  作者：Alan Whitehead、Matthew D. McReynolds、Joel D. Moore、Paul R. Hanson

  DOI：10.1021/ol0512886

  日期：2005.7.1

  A new tether for small molecule synthesis is reported. This functionally active tether mediates the desymmetrization of a pseudo-C-2-symmetric tris-allylic phosphate triester to generate a P-chiral bicyclo[4.3.1]phosphate containing ample steric and stereoelectronic differentiation for investigating chemo-, regio-, and stereoselective transformations. Overall, the method reported herein demonstrates a fundamentally new role of phosphates in synthesis and provides differentiated polyol building blocks for use in natural product synthesis.