[(E)-1-Cyano-5-methyl-6-(tetrahydro-pyran-2-yloxy)-hex-4-enyl]-phosphonic acid diethyl ester | 202338-89-4

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机膦酸及其衍生物
• 英文名称: [(E)-1-Cyano-5-methyl-6-(tetrahydro-pyran-2-yloxy)-hex-4-enyl]-phosphonic acid diethyl ester
• 英文别名: (E)-2-diethoxyphosphoryl-6-methyl-7-(oxan-2-yloxy)hept-5-enenitrile
• CAS: 202338-89-4
• 化学式: C₁₇H₃₀NO₅P
• 分子量: 359.403
• InChiKey: MOZQTCUBCLQDCK-OQLLNIDSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  24
• 可旋转键数：
  11
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  77.8
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  [(E)-1-Cyano-5-methyl-6-(tetrahydro-pyran-2-yloxy)-hex-4-enyl]-phosphonic acid diethyl ester 在 sodium periodate 、 4-甲基苯磺酸吡啶 、 三乙胺 、 甲基磺酸酐 作用下， 以 甲醇 、 二氯甲烷 、 水 、 乙腈 为溶剂， 反应 18.42h， 生成 (2Z)-(4S)-4-benzyloxy-2-[(E)-5-bromo-4-methylpent-3-enyl]octa-2,7-dienenitrile
  参考文献：
  名称：

  Divergent synthesis of pseudoenantiomers for ABC-ring moiety of steroids

  摘要：

  Steroid family has various bioactivities and characteristic polycyclic structure. Although several synthetic methods have been reported, more efficient way is desired for medicinal chemistry. In this Letter, we synthesized pseudoenantiomers of tricyclic enones toward both enantiomers for ABC-ring moiety of steroids utilizing D-mannitol as a chiral source. The key steps are radical domino cyclization of polyalkenyl-beta-keto ester into tricyclic keto ester and subsequent dealkoxycarbonylation. (C) 2014 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2014.04.018
• 作为产物：
  描述：

  5-溴-2-甲基-2-戊烯 在 叔丁基过氧化氢 、 selenium(IV) oxide 、 对甲苯磺酸 作用下， 生成 [(E)-1-Cyano-5-methyl-6-(tetrahydro-pyran-2-yloxy)-hex-4-enyl]-phosphonic acid diethyl ester
  参考文献：
  名称：

  多环系统中角电泳的分子内自由基方法

  摘要：

  已经通过含有α，β-不饱和电泳的多烯8的立体选择性氧化性自由基环化反应实现了在多环系统9中引入有角C-8氰基基团。

  DOI：

  10.1016/0040-4039(96)00167-0

文献信息

• Application of a Radical Methodology toward the Synthesis of <i>d,l</i>-5α-Pregnanes and Related Steroids:  A Stereoselective Radical Cascade Approach
  作者：Phillip A. Zoretic、Haiquan Fang、Anthony A. Ribeiro

  DOI：10.1021/jo980518+

  日期：1998.10.1

  A stereoselective radical cascade cyclization to 5alpha-pregnanes is presented. Oxidative free radical cyclization of an appropriately substituted chloro cyano ester polyene was used to introduce the all trans stereochemistry in the steroid nucleus. The cyano group was utilized to introduce a C-8beta angular hydrogen, while the chloro ester moiety served as an entry to the geminal hydrogens at C-4

  提出了立体选择性自由基级联环化成5α-孕烷。适当取代的氯氰基酯多烯的氧化性自由基环化被用来在类固醇核中引入全反式立体化学。氰基用于引入C-8β角氢，而氯酯部分则作为C-4上双氢的入口。
• A radical prototype to steroids: Synthesis of d,l-5α-D-homoandrostane-4α-methyl-3,17a-dione
  作者：Phillip A. Zoretic、Zhiyue Chen、Yongzheng Zhang、Anthony A. Ribeiro

  DOI：10.1016/0040-4039(96)01793-5

  日期：1996.10

  An intramolecular radical methodology is described as an approach to D-homoandrostanes. The angular C-8 cyano group in tetracycle 7 derived from radical cyclization of polyene 6 serves as a latent functional group for elaboration to the C-8 βH in d,l-homoandrostane 11.

  分子内自由基方法学被描述为D-高雄烷酮的一种方法。来自多烯6的自由基环化的四环7中的角C-8氰基基团是潜在的官能团，用于修饰d，l-高雄甾烷11中的C- 8βH 。
• Advanced Tetracycles in a Stereoselective Approach to <i>d,l</i>-Spongiatriol and Related Metabolites:  The Use of Radicals in the Synthesis of Angular Electrophores
  作者：Phillip A. Zoretic、Yongzheng Zhang、Haiquan Fang、Anthony A. Ribeiro、George Dubay

  DOI：10.1021/jo971632f

  日期：1998.2.1

  A stereoselective radical cascade cyclization of polyene 6, containing an alpha,beta-unsaturated cyano group, was employed to control six contiguous chiral centers and to introduce a C-8 angular CN group in tricycle 7, The cyano group was ultimately utilized as an entry to a C-8 angular hydroxymethyl group, Compound 7 was converted inter two key tetracycles 22 and 25, respectively, each possessing an intact D-furan ring system and containing the necessary functionality for further chemical elaboration to the highly oxygenated spongians 1-5.
• Divergent synthesis of pseudoenantiomers for ABC-ring moiety of steroids
  作者：Miyu Furuta、Kengo Hanaya、Takeshi Sugai、Mitsuru Shoji

  DOI：10.1016/j.tetlet.2014.04.018

  日期：2014.5

  Steroid family has various bioactivities and characteristic polycyclic structure. Although several synthetic methods have been reported, more efficient way is desired for medicinal chemistry. In this Letter, we synthesized pseudoenantiomers of tricyclic enones toward both enantiomers for ABC-ring moiety of steroids utilizing D-mannitol as a chiral source. The key steps are radical domino cyclization of polyalkenyl-beta-keto ester into tricyclic keto ester and subsequent dealkoxycarbonylation. (C) 2014 Elsevier Ltd. All rights reserved.
• An intramolecular radical approach to angular electrophores in polycyclic systems
  作者：Phillip A. Zoretic、Yongzheng Zhang、Anthony A. Ribeiro

  DOI：10.1016/0040-4039(96)00167-0

  日期：1996.3

  The introduction of an angular C-8 cyano group in polycyclic system 9 has been realized via a stereoselective oxidative radical cyclization of polyene 8 containing an α,β-unsaturated electrophore.

  已经通过含有α，β-不饱和电泳的多烯8的立体选择性氧化性自由基环化反应实现了在多环系统9中引入有角C-8氰基基团。