4-(2,2,2-trimethylacetoxy)methyl-4-phenyl-1,6-heptadiene | 250606-42-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 4-(2,2,2-trimethylacetoxy)methyl-4-phenyl-1,6-heptadiene
• 英文别名: (2-Phenyl-2-prop-2-enylpent-4-enyl) 2,2-dimethylpropanoate
• CAS: 250606-42-9
• 化学式: C₁₉H₂₆O₂
• 分子量: 286.414
• InChiKey: HGOJZXBEWHXVIK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.5
• 重原子数：
  21
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4-(2,2,2-trimethylacetoxy)methyl-4-phenyl-1,6-heptadiene 在 三乙基硅烷 、 (η(3)-allyl)PdCl * tricyclohexylphosphine 、 四(3,5-二(三氟甲基)苯基)硼酸钠 作用下， 以 二氯甲烷 为溶剂， 反应 0.33h， 以89%的产率得到4-trimethylacetoxymethyl-1,2-dimethyl-4-phenylcyclopentene
  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：

  4-hydroxymethyl-4-phenyl-1,6-heptadiene 、 三甲基乙酰氯 在 4-二甲氨基吡啶 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 以70%的产率得到4-(2,2,2-trimethylacetoxy)methyl-4-phenyl-1,6-heptadiene
  参考文献：
  名称：

  Silane-Promoted Cycloisomerization of Functionalized 1,6-Dienes Catalyzed by a Cationic (π-Allyl)palladium Complex

  摘要：

  [GRAPHICS]A 1:1 mixture of the (pi-allyl)palladium complex (eta(3)-C3H5)Pd(Cl)PCy3 and NaB[3,5-C6H3(CF3)(2)](4) in the presence of HSiEt3 catalyzed the cycloisomerization of functionalized 1,6-dienes to form 1,2-disubstituted cyclopentenes in good yield with high selectivity (typically >94%). The protocol tolerated a range of functional groups and substitution at one of the allylic carbon atoms.

  DOI：

  10.1021/ol9908981

文献信息

• Palladium-Catalyzed Asymmetric Diene Cyclization/Hydrosilylation Employing Functionalized Silanes and Disiloxanes
  作者：Tao Pei、Ross A. Widenhoefer

  DOI：10.1021/jo015724n

  日期：2001.11.1

  diallylmalonate (1) and other functionalized 1,6-dienes in the presence of a catalytic 1:1 mixture of (N-N)Pd(Me)Cl [N-N = (R)-(+)-4-isopropyl-2-(2-pyridinyl)-2-oxazoline] [(R)-2] and NaBAr(4) [Ar = 3,5-C(6)H(3)(CF(3))(2)] to form the corresponding silylated cyclopentanes in good yield with high diastereoselectivity. The enantioselectivity of cyclization/hydrosilylation of 1 with disiloxanes and functionalized

  HSiMe（2）CH（x）Ph（3-x）（x = 1或2）形式的五取代二硅氧烷和硅烷与二烯丙二酸二甲酯（1）和其他功能化的1,6-二烯在催化1存在下反应：1（NN）Pd（Me）Cl [NN =（R）-（+）-4-异丙基-2-（2-吡啶基）-2-恶唑啉] [（R）-2]和NaBAr（4 ）[Ar = 3,5-C（6）H（3）（CF（3））（2）]以高收率和高非对映选择性形成相应的甲硅烷基化环戊烷。1在20摄氏度下与二硅氧烷和官能化硅烷的1的环化/氢化硅烷化的对映选择性按以下顺序增加：HSiMe（2）OSiMe（3）（75％ee）
• Asymmetric diene cyclization/hydrosilylation/oxidation employing 1-tert-butyl-3,3-dimethyl-1,1-diphenyldisiloxane
  作者：Tao Pei、Ross A Widenhoefer

  DOI：10.1016/s0040-4039(00)01321-6

  日期：2000.9

  A 1:1 mixture of (NN)Pd(Me)Cl [NN=(R)-(+)-4-isopropyl-2-(2-pyridinyl)-2-oxazoline] (1) and NaBAr4 [Ar=3,5-C6H3(CF3)2] catalyzed the asymmetric cyclization/hydrosilylation of functionalized 1,6-dienes with 1-tert-butyl-3,3-dimethyl-1,1-diphenyldisiloxane at −20°C to form silylated cyclopentanes in good yield with up to 95% ee. These silylated carbocycles underwent oxidative cleavage of the CSi bond

  （NN）Pd（Me）Cl [NN=（R）-（+）-4-异丙基-2-（2-吡啶基）-2-恶唑啉]（1）和NaBAr的1：1混合物4 [Ar = 3,5-C 6 H 3（CF 3）2 ]催化官能化的1,6-二烯与1-叔丁基-3,3-二甲基-1,1-二苯基二硅氧烷的不对称环化/氢化硅烷化-20°C形成高收率ee高达95％ee的甲硅烷基化环戊烷。这些甲硅烷基化的碳环在室温下通过H 2 O 2进行CSi键的氧化裂解，形成相应的醇。