(PhCO)(Ph)C(CH2CH=CH2)2 | 41848-55-9

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: (PhCO)(Ph)C(CH2CH=CH2)2
• 英文别名: 4-Phenyl-4-benzoyl-1,6-heptadien；1,2-Diphenyl-2-prop-2-enylpent-4-en-1-one
• CAS: 41848-55-9
• 化学式: C₂₀H₂₀O
• 分子量: 276.378
• InChiKey: SIZWWCOSURFXKE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  21
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.15
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (PhCO)(Ph)C(CH2CH=CH2)2 在 三乙基硅烷 、 (η-C3H5)Pd(Cl)P(cyclopentyl)3 、 四(3,5-二(三氟甲基)苯基)硼酸钠 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 0.33h， 以95%的产率得到1,2-dimethyl-4-phenyl-4-benzoylcyclopentene
  参考文献：
  名称：

  Development, Synthetic Scope, and Mechanistic Studies of the Palladium-Catalyzed Cycloisomerization of Functionalized 1,6-Dienes in the Presence of Silane

  摘要：

  A 1:1 mixture of the pi-allyl palladium complex (eta (3)-C3H5)Pd(CI)PCy3 Cia) and NaB[3,5-C6H3(CF3)(2)](4) in the presence of HSiEt3 catalyzed the cycloisomerization of diethyl diallylmalonate (2b) to form 4,4-dicarbomethoxy 1,2-dimethylcyclopentane (3b) in 98% yield with 98% isomeric purity. The procedure tolerated a range of functionality including esters, ketones, sulfones, protected alcohols, and substitution at the allylic and terminal olefinic carbon atoms. Cycloisomerization of 2b obeyed zero-order kinetics to >3 half-lives with initial formation of 1,1-dicarboethoxy-4-methyl-3-methylenecyclopentane (4b), followed by secondary isomerization to 3b. Deuterium labeling studies revealed that the conversion of 2b to 4b was accompanied by significant H/D exchange, consistent with an addition/elimination pathway coupled with facile H/D exchange of the Pd-H(D) intermediates with free silane.

  DOI：

  10.1021/ja001730+
• 作为产物：
  描述：

  、 烯丙醇 在 四(三苯基膦)钯 、 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 生成 3-allyl-3-phenyl-5-hexen-2-one 、 (PhCO)(Ph)C(CH2CH=CH2)2
  参考文献：
  名称：

  Deacylative Allylation：通过 Retro-Claisen 激活进行烯丙基烷基化

  摘要：

  本文描述了多种相对不稳定的碳亲核试剂的烯丙基烷基化的新方法。在这个“脱酰基烯丙基化”过程中，偶联伙伴，烯丙醇和酮亲核试剂，进行原位逆克莱森活化以生成烯丙乙酸和碳负离子。在钯的存在下，这些反应性中间体进行催化偶联形成新的 CC 键。与单分子脱羧烯丙基化（一种常用的碳阴离子烯丙基化方法）相比，脱酰基烯丙基化是一种分子间过程。此外，脱酰基烯丙基化允许容易获得的烯丙醇直接偶联。最后，通过快速构建多种 1、

  DOI：

  10.1021/ja205717f

文献信息

• Cyclization/Hydrogermylation of Functionalized 1,6-Dienes Catalyzed by Cationic Palladium Complexes
  作者：Ross A. Widenhoefer、Anand Vadehra、Pavan K. Cheruvu

  DOI：10.1021/om990546y

  日期：1999.10.1

  A 1:1 mixture of the palladium phenanthroline complex (phen)Pd(Me)Cl and NaBAr4 (phen = 1,10-phenanthroline; Ar = 3,5-C6H3(CF3)2) catalyzed the reaction of 4,4-disubstituted 1,6-dienes with trialkylgermanes at 80 °C in 1,2-dichloroethane (DCE) to form R3GeCH2-substituted cyclopentanes in good yield with high trans selectivity.

  钯菲咯啉配合物（phen）Pd（Me）Cl和NaBAr 4的1：1混合物（phen = 1,10-菲咯啉; Ar = 3,5-C 6 H 3（CF 3）2）催化了在1,2-二氯乙烷（DCE）中，在80°C下，具有三烷基锗烷的4,4-二取代的1,6-二烯以高收率和高反式选择性形成R 3 GeCH 2取代的环戊烷。
• Cyclization/Hydrosilylation of Functionalized Dienes Catalyzed by a Cationic Palladium Phenanthroline Complex
  作者：Ross A. Widenhoefer、Carmine N. Stengone

  DOI：10.1021/jo9913006

  日期：1999.11.1

  Mixtures of(phen)PdMe2 (2a) and HBAr'(4) (3a) or (phen)PdMe(Cl) (2b) and NaBAr'(4) (3b) [phen = 1, 10-phenanthroline; Ar' = 3,5-C6H3(CF3)(2)] catalyzed the cyclization/hydrosilylation of functionalized 1,6-dienes to form silylated cyclopentanes in good yield and with excellent trans selectivity about the newly formed C-C bond (typically >50:1). A range of tertiary hydrosilanes were employed in the procedure although unhindered trialkylsilanes provided the most consistent results. The protocol tolerated a range of polar functionality including esters, ethers, amides, sulfones, and cyano groups. 4,4-Disubstitution on the diene backbone promoted cyclization, and a homoallylic ester, ketone, or ether directing group was required for efficient cyclization. The procedure tolerated dienes which possessed a single trans-substituted olefin and also tolerated allylic substitution. These substituted dienes underwent cyclization/hydrosilylation to form carbocycles resulting from transfer of the silyl group to the less hindered olefin. Mixtures of 2a and 3a also catalyzed the cyclization/hydrosilylation of functionalized 1,7-dienes to form silylated cyclohexane derivatives. Cyclization/hydrosilylation of 1,7-dienes was typically slower, less stereoselective, and more sensitive to substitution than was cyclization of 1,6-dienes.
• An improved catalyst for the cyclization/hydrosilylation of functionalized 1,6-dienes employing dimethylphenylsilane
  作者：Ross A. Widenhoefer、Anand Vadehra

  DOI：10.1016/s0040-4039(99)01706-2

  日期：1999.12

  A 1:1 mixture of (Me-4-phen)Pd(Me)Cl [Me-4-phen=3,4,7,8-tetramethyl- 1,10-phenanthroline] and NaBAr4 [Ar=3,5-C6H3(CF3)(2)] catalyzed the cyclization/hydrosilylation of functionalized 1,6-dienes with dimethylphenylsilane within minutes at room temperature to form silylated cyclopentanes in good yield with high trans-selectivity. (C) 1999 Elsevier Science Ltd. All rights reserved.