正膦,5-己烯亚基三苯基- | 111219-94-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 正膦,5-己烯亚基三苯基-
• 英文名称: 5-Hexenyl(triphenyl)phosphorane
• 英文别名: hex-5-enylidene(triphenyl)-λ5-phosphane
• CAS: 111219-94-4
• 化学式: C₂₄H₂₅P
• 分子量: 344.436
• InChiKey: RIJANPAWECFBLR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  25
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  正膦,5-己烯亚基三苯基- 在 palladium dichloride 吡啶 、 盐酸 、 水 、 氧气 、 copper(l) chloride 作用下， 以 四氢呋喃 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 87.0h， 生成 (8S,6E)-8-hydroxy-9-[(4-methylbenzenesulfonyl)oxy]-6-nonen-2-one
  参考文献：
  名称：

  Samarium(II) Iodide-Mediated Reductive Annulations of Ketones Bearing a Distal Vinyl Epoxide Moiety

  摘要：

  Samarium(II) iodide in the presence of hexamethylphosphoramide (HMPA) efficiently promotes the intramolecular coupling of ketones with distal epoxy olefins. The reaction appears to proceed by a mechanism wherein a ketyl couples with the unsaturated epoxide. Subsequent fragmentation of the epoxide ring in compounds 1a-k yields carbocycles 2a-k with an allyl alcohol side chain in good yields, and often with high diastereoselectivity. When tetramethylguanidine was used as an additive instead of HMPA, the desired carbocycle was obtained in good yield, but the diastereoselectivity was diminished. A palladium(0)-catalyzed SmI2 reaction provided the expected product in modest yield, but the sense of diastereoselectivity was reversed. In the latter case, a different reaction mechanism may be involved. Thus, formation of an allylsamarium species may be invoked, with nucleophilic carbonyl addition leading to the observed facial selectivity.

  DOI：

  10.1021/jo960335s
• 作为产物：
  描述：

  5-己烯-1-醇 在 咪唑 、 碘 、 苯基锂 、 三苯基膦 作用下， 以 乙腈 为溶剂， 反应 1.0h， 生成 正膦,5-己烯亚基三苯基-
  参考文献：
  名称：

  Samarium(II) Iodide-Mediated Reductive Annulations of Ketones Bearing a Distal Vinyl Epoxide Moiety

  摘要：

  Samarium(II) iodide in the presence of hexamethylphosphoramide (HMPA) efficiently promotes the intramolecular coupling of ketones with distal epoxy olefins. The reaction appears to proceed by a mechanism wherein a ketyl couples with the unsaturated epoxide. Subsequent fragmentation of the epoxide ring in compounds 1a-k yields carbocycles 2a-k with an allyl alcohol side chain in good yields, and often with high diastereoselectivity. When tetramethylguanidine was used as an additive instead of HMPA, the desired carbocycle was obtained in good yield, but the diastereoselectivity was diminished. A palladium(0)-catalyzed SmI2 reaction provided the expected product in modest yield, but the sense of diastereoselectivity was reversed. In the latter case, a different reaction mechanism may be involved. Thus, formation of an allylsamarium species may be invoked, with nucleophilic carbonyl addition leading to the observed facial selectivity.

  DOI：

  10.1021/jo960335s

文献信息

• Synthetic Studies towards Radicicol through Biomimetic Macrolactonization and Transannular Aromatization Reactions
  作者：Rosa Cookson、Christoph Pöverlein、Jennifer Lachs、Anthony G. M. Barrett

  DOI：10.1002/ejoc.201402205

  日期：2014.7

  Studies towards the total synthesis of the natural product radicicol are described that employ a late-stage esterification and aromatization by trapping a ketene intermediate. The subsequent biomimetic aromatization of the resultant triketo ester gave highly functionalized resorcylates. Two distinct methods were examined that trap the ketene intermediate through either an intermolecular or intramolecular

  描述了对天然产物 radicicol 全合成的研究，该研究通过捕获乙烯酮中间体采用后期酯化和芳构化。随后所得三酮酯的仿生芳构化得到高度官能化的间苯二甲酸酯。研究了通过分子间或分子内过程捕获乙烯酮中间体的两种不同方法。在第一种方法中，间苯二甲酸酯的合成之后是闭环复分解，这将大环内酯和受保护的前体提供给单霉素 I。在第二种方法中，检测了分子内烯酮捕获作为关闭大环并形成间苯二酸酯大环内酯。这些研究展示了各种耐受芳构化反应条件的敏感官能团，
• Mitra, R. B.; Reddy, G. Bhasker, Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 1988, vol. 27, # 1-12, p. 691 - 692
  作者：Mitra, R. B.、Reddy, G. Bhasker

  DOI：——

  日期：——
• Reddy, G. Bhaskar; Mitra, R. B., Synthetic Communications, 1987, vol. 17, # 7, p. 893 - 900
  作者：Reddy, G. Bhaskar、Mitra, R. B.

  DOI：——

  日期：——
• Efforts toward the Synthesis of Pseudolaric Acid A: Intramolecular Bromoetherification as a Multipurpose Synthetic Tool
  作者：Leo A. Paquette、Jeremy D. Pettigrew

  DOI：10.3987/com-09-s(s)7

  日期：——

  Regioselective double bond cleavage within 5, required for access to the trans-fused perhydroazulene framework of pseudolaric acid A (1), has been accomplished via a highly diastereoselective intramolecular bromoetherification process, the latter serving a dual role as a protecting group tactic.
• MITRA, R. B.;REDDY, G. BHASKER, INDIAN J. CHEM. B, 27,(1988) N 7, C. 691-692
  作者：MITRA, R. B.、REDDY, G. BHASKER

  DOI：——

  日期：——