α,α-diallyl-δ-valerolactone | 163012-19-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: α,α-diallyl-δ-valerolactone
• 英文别名: tetrahydro-3,3-bis(2-propenyl)pyran-2(2H)-one；3,3-diallyl-tetrahydropyran-2-one；3,3-Diallyltetrahydro-2H-pyran-2-one；3,3-bis(prop-2-enyl)oxan-2-one
• CAS: 163012-19-9
• 化学式: C₁₁H₁₆O₂
• 分子量: 180.247
• InChiKey: HIZNCUMVMZLFEM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.55
• 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：

  α,α-diallyl-δ-valerolactone 在 4-二甲氨基吡啶 、 5% Pd(II)/C(eggshell) 、 氢气 、 三甲基铝 、 sodium hydride 、 三乙胺 作用下， 以 四氢呋喃 、 乙醇 、 二氯甲烷 为溶剂， -78.0~20.0 ℃ 、133.32 Pa 条件下， 反应 28.5h， 生成 methyl 2,2-dipropylpyrrolidine-1-carboxylate
  参考文献：
  名称：

  的光化学重排Ñ -Mesyloxylactams：立体专一形成Ñ -Heterocycles

  摘要：

  N-甲氧基内酰胺类对各种环大小的N-杂环进行有效的环收缩。产率随羰基的取代度α而增加。保留了手性迁移碳的立体化学信息，使该反应成为众所周知的霍夫曼，库尔蒂乌斯，洛森和施密特重排的合成有用补充。

  DOI：

  10.1021/jo101805q
• 作为产物：
  描述：

  delta-戊内酯 在 六甲基磷酰三胺 、 lithium diisopropyl amide 作用下， 反应 7.0h， 生成 α,α-diallyl-δ-valerolactone
  参考文献：
  名称：

  Sequenced Reactions with Samarium(II) Iodide. Tandem Intramolecular Nucleophilic Acyl Substitution/Intramolecular Barbier Cyclizations

  摘要：

  Samarium(II) iodide has been employed to promote a tandem intramolecular nucleophilic acyl substitution/intramolecular Barbier cyclization sequence, generating bicyclic and tricyclic ring systems in excellent yield and high diastereoselectivity. Additionally, a highly versatile ring expansion-cyclization sequence allows entry into several different naturally occurring tricyclic ring systems containing seven- and eight-membered rings.

  DOI：

  10.1021/ja00118a007

文献信息

• Studies on the Mechanism, Selectivity, and Synthetic Utility of Lactone Reduction Using SmI₂ and H₂O
  作者：Dixit Parmar、Lorna A. Duffy、Dhandapani V. Sadasivam、Hiroshi Matsubara、Paul A. Bradley、Robert A. Flowers、David J. Procter

  DOI：10.1021/ja906396u

  日期：2009.10.28

  esters and lactones have long been thought to lie outside the reducing range of SmI(2), activation of the lanthanide reagent by H(2)O allows some of these substrates to be manipulated in an unprecedented fashion. For example, the SmI(2)-H(2)O reducing system shows complete selectivity for the reduction of 6-membered lactones over other classes of lactones and esters. The kinetics of reduction has been

  尽管长期以来一直认为简单的脂肪族酯和内酯位于 SmI(2) 的降低范围之外，但 H(2)O 对镧系元素试剂的激活允许以前所未有的方式操纵其中的一些底物。例如，SmI(2)-H(2)O 还原系统显示出相对于其他类别的内酯和酯还原 6 元内酯的完全选择性。使用停流分光光度法研究了还原动力学。实验和计算研究表明选择性的起源在于初始电子转移到内酯羰基。在用 SmI(2)-H(2)O 进行内酯还原过程中形成的自由基中间体可用于环化，以提供具有高非对映选择性的环状酮（或缩酮）产品。
• Stereocontrolled total synthesis of (±)-ptaquilosin, the aglycone of ptaquiloside, a bracken carcinogen
  作者：Hideo Kigoshi、Akihiko Sawada、Yoshisuke Nakayama、Haruki Niwa、Kiyoyuki Yamada

  DOI：10.1016/s0040-4039(00)99630-8

  日期：——

  Starting from α-allyl-δ-valerolactone, stereocontrolled synthesis of ptaquilosin (2), the aglycone of a bracken carcinogen ptaquiloside (1) has been achieved in racemic form, which includes a novel deformylation-hydroxylation reaction (21 → 23) as one of the key steps.

  从α-烯丙基-δ-戊内酯开始，立体合成ptaquilosin（2），已获得外消旋形式的蕨类致癌物pquiquiloside（1）的糖苷配基，其中包括一个新颖的甲酰化-羟基化反应（21 → 23）。关键步骤。
• Fluid, stable interpolymer/polyol compositions, process for the production thereof and processes for the production of elastomeric polyurethanes and polyurethane foams therefrom
  申请人：UNION CARBIDE CORPORATION

  公开号：EP0006605A1

  公开（公告）日：1980-01-09

  Fluid, stable polymer-polyols are provided which consist of an organic polyol medium and an interpolymer of a minor amount of polymerized ethylenically unsaturated dicarboxylic acid anhydride, such as maleic acid anhydride, and a major amount of at least one different polymerized ethylenically unsaturated monomer, the interpolymer being in the form of particles that are stably dispersed in the polyol. Polyurethane foams produced from these polymer/ polyols display improved load bearing and compression set when compared with polymer/polyols produced in a similar manner without the ethylenically unsaturated dicarboxylic acid anhydride: elastomers so produced have improved tensile modulus and tear properties.

  提供了流体稳定聚合物多元醇，它由有机多元醇介质和少量聚合乙烯基不饱和二羧酸酐（如马来酸酐）与大量至少一种不同的聚合乙烯基不饱和单体的互聚物组成，互聚物呈颗粒状稳定地分散在多元醇中。与不含乙烯基不饱和二羧酸酐的聚合物/多元醇相比，用这些聚合物/多元醇生产的聚氨酯泡沫塑料的承载能力和压缩永久变形都有所改善：用这种方法生产的弹性体具有更好的拉伸模量和撕裂性能。
• Aliphatic Polyesters with Pendant Cyclopentene Groups:  Controlled Synthesis and Conversion to Polyester-<i>g</i><i>raft</i>-PEG Copolymers
  作者：Bryan Parrish、Todd Emrick

  DOI：10.1021/ma048981d

  日期：2004.8.1
• A Ring Size-Selective Reduction of Lactones Using SmI₂ and H₂O
  作者：Lorna A. Duffy、Hiroshi Matsubara、David J. Procter

  DOI：10.1021/ja078137d

  日期：2008.1.30

  The Sml(2)-H2O reducing systems shows complete selectivity for six-membered lactones over other classes of lactone and esters. Experimental and computational studies suggest that the origin of the selectivity lies in the initial electron-transfer to the lactone carbonyl.