δ,δ-Diallyl-δ-valerolactone | 87998-07-0

• 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: δ,δ-Diallyl-δ-valerolactone
• 英文别名: 6,6-diallyltetrahydro-2H-pyran-2-one；6,6-diallyltetrahydropyran-2-one；5-Allyl-7-octen-5-olide；6,6-Bis(prop-2-enyl)oxan-2-one
• CAS: 87998-07-0
• 化学式: C₁₁H₁₆O₂
• 分子量: 180.247
• InChiKey: KWIXEXOMEQPSRT-UHFFFAOYSA-N

物化性质

• 沸点：
  100-105 °C(Press: 0.001 Torr)
• 密度：
  0.944±0.06 g/cm3(Predicted)

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：

  δ,δ-Diallyl-δ-valerolactone 在 titanium(IV) isopropylate 、 Grubbs catalyst first generation 作用下， 以 二氯甲烷 为溶剂， 反应 6.0h， 以79%的产率得到6-oxa-spiro[4.5]dec-2-en-7-one
  参考文献：
  名称：

  Efficient synthesis of spirolactones from cyclic anhydrides via an allylation/alkylation-RCM sequence

  摘要：

  Starting from cyclic anhydrides the diallyl or dibutenyl lactones were obtained. The ring closing metathesis reaction of these using the Grubbs catalyst provided the corresponding spirolactones in good yields. With diallyl delta-lactone 2h, RCM occurred only in the presence of titanium tetraisopropoxide. (C) 2000 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0022-328x(00)00330-2
• 作为产物：
  描述：

  戊二酸酐 、 triallylaluminum 以 四氢呋喃 为溶剂， 反应 0.5h， 以71%的产率得到δ,δ-Diallyl-δ-valerolactone
  参考文献：
  名称：

  An efficient of Grignard-type procedure for the preparation of gem-diallylated compound

  摘要：

  An efficient and a new procedure for the conversion of various carboxylic acid derivatives into the corresponding gemdiallylated compound under mild reaction condition has been developed. The triallyaluminum mediated Grignard-type addition of carboxylic acid derivative was utilized as a key operation to affect the transformation. The procedure is operationally simple, giving good to excellent product yields for a broad range of substrates. The chemoselectivity and regioselectivity of triallylaluminum were also demonstrated. (C) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2007.07.008

文献信息

• Lactone Radical Cyclizations and Cyclization Cascades Mediated by SmI₂–H₂O
  作者：Dixit Parmar、Hiroshi Matsubara、Kieran Price、Malcolm Spain、David J. Procter

  DOI：10.1021/ja3047975

  日期：2012.8.1

  Unsaturated lactones undergo reductive radical cyclizations upon treatment with SmI(2)-H(2)O to give decorated cycloheptanes in a single highly selective operation during which up to three contiguous stereocenters are generated. Furthermore, cascade processes involving lactones bearing two alkenes, an alkene and an alkyne, or an allene and an alkene allow "one-pot" access to biologically significant

  不饱和内酯在用 SmI(2)-H(2)O 处理后会发生还原自由基环化，以在单个高度选择性的操作中提供装饰的环庚烷，在此期间生成最多三个连续的立体中心。此外，涉及带有两个烯烃、一个烯烃和一个炔烃，或一个丙二烯和一个烯烃的内酯的级联过程允许“一锅”访问具有生物学意义的分子支架，最多可构建四个连续的立体中心。环化通过捕获由内酯羰基的电子转移还原形成的自由基阴离子而进行。
• Brønsted Acid Catalyzed Enantioselective Semipinacol Rearrangement for the Synthesis of Chiral Spiroethers
  作者：Qing-Wei Zhang、Chun-An Fan、Hai-Jun Zhang、Yong-Qiang Tu、Yu-Ming Zhao、Peiming Gu、Zhi-Min Chen

  DOI：10.1002/anie.200904565

  日期：2009.10.26

  A new twist: The catalytic asymmetric semipinacol rearrangement reaction of 2‐oxo allylic alcohols 1 in the presence of a catalytic amount of chiral phosphoric acid (R)‐2 a or its silver salt (R)‐2 b affords enantiomerically pure spiroethers 3.

  一个新的转折：2-氧代烯丙醇的催化不对称semipinacol重排反应1在手性磷酸（催化量存在- [R ）- 2或它的银盐（[R ）- 2 B，得到对映体纯spiroethers 3。
• Reductive Cyclization Cascades of Lactones Using SmI₂−H₂O
  作者：Dixit Parmar、Kieran Price、Malcolm Spain、Hiroshi Matsubara、Paul A. Bradley、David J. Procter

  DOI：10.1021/ja1114908

  日期：2011.3.2

  Lactones bearing two alkenes or an alkene and an alkyne undergo reductive cyclization cascades upon treatment with SmI(2)-H(2)O, giving decorated azulene motifs in excellent yields with good diastereocontrol.

  带有两个烯烃或一个烯烃和一个炔烃的内酯在用 SmI(2)-H(2)O 处理后会发生还原环化级联，从而以优异的产量和良好的非对映控制提供装饰的 azulene 图案。
• Unsymmetrical Ketone Synthesis via a Three-Component Connection Reaction of Organozincs, Allylating Agents, and Carbon Monoxide
  作者：Kengo Yasui、Keigo Fugami、Shuji Tanaka、Yoshinao Tamaru

  DOI：10.1021/jo00110a047

  日期：1995.3

  A wide variety of organozincs (diethylzinc, alkylzinc halides, and organozincs 2, 5, and 9a-e, functionalized with ester and nitrile groups) undergo a three-component connection reaction with carbon monoxide and allylic benzoates or phosphates 1a-h to furnish unsymmetrical ketones, e.g., 3, 6, and 10, in good yields under 1 atm of carbon monoxide at ambient temperature by the catalysis of tetrakis(triphenylphosphine)palladium in THF/HMPA. The regio- and stereoselectivities of the present carbonylation show marked contrast to those reported for the palladium-catalyzed carbonylation of unsymmetrical allylic substrates. For example, the reaction of crotyl benzoate with octylzinc iodide provides all the possible stereo- and regioisomers, i.e., cis- and trans-2-butenyl and 1-methyl-2-propenyl octyl ketones in comparable amounts. The carbonylative coupling of carvyl phosphates, trans- and cis-1h, and gamma-zincio ester 5 is stereospecific and proceeds with inversion of configuration at the allylic stereocenters to furnish cis- and trans-6h, respectively, as single diastereomers. In the absence of HMPA, the reaction feature changes dramatically and lactones 12 and 13 (composed of organozincs, carbon monoxide, and allylating agents in the ratios of 1:1:2 and 2:1:1, respectively) and symmetrical keto diesters 14 (composed of 2 mol of organozincs and 1 mol of carbon monoxide) are formed in varying ratios depending on the reaction conditions. Synthetic scope of the unsymmetrical ketones and mechanistic rationale for these unique and unprecedented reaction behaviors are discussed.
• δ-Substituted Organoalkaline Metal Compounds; Preparation and Synthetic Applications
  作者：José Barluenga、José R. Fernandez、Josefa Florez、Miguel Yus

  DOI：10.1055/s-1983-30493

  日期：——