methyl Z-3-(diethylphosphoryloxy)-7-methyl-2,6-octadienoate | 88218-59-1

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: methyl Z-3-(diethylphosphoryloxy)-7-methyl-2,6-octadienoate
• 英文别名: methyl (Z)-3-((diethoxyphosphoryl)oxy)-7-methylocta-2,6-dienoate；methyl (2Z)-3-diethoxyphosphoryloxy-7-methylocta-2,6-dienoate
• CAS: 88218-59-1
• 化学式: C₁₄H₂₅O₆P
• 分子量: 320.323
• InChiKey: OWXJYQBARGTKDD-QBFSEMIESA-N

物化性质

• 沸点：
  379.7±42.0 °C(Predicted)
• 密度：
  1.092±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  21
• 可旋转键数：
  11
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  71.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  methyl Z-3-(diethylphosphoryloxy)-7-methyl-2,6-octadienoate 在 potassium osmate(VI) 、 甲基磺酰胺 bis(acetylacetonate)nickel(II) 、 lithium aluminium tetrahydride 、 (DHQD)2PHAL 、 三氟化硼乙醚 、 potassium carbonate 、 三乙胺 、 potassium hexacyanoferrate(III) 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 水 、 叔丁醇 为溶剂， 反应 35.0h， 生成 (1RS,3SR)-3-(hydroxymethyl)-2,2-dimethyl-4-methylenecyclohexanol
  参考文献：
  名称：

  Enantioselective synthesis of both enantiomers of γ-ionone, γ-damascone, karahana lactone and karahana ether

  摘要：

  A straightforward enantioselective synthesis of both enantiomers of the title compounds is described starting from enantiopure methyl (2S,6R)- or (2R,6S)-cis-2-hydroxy-gamma-cyclogeraniate. These versatile building blocks are obtained by biomimetic cyclization of methyl (6S)- or (6R)-(Z)-6,7-epoxy-7-methyl-3-(trimethylsilyl)methyl-2-octenoate, respectively. The chiral information was encoded by a highly regioselective Sharpless asymmetric dihydroxylation of the corresponding diene. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(02)00335-x
• 作为产物：
  描述：

  1-溴-3-甲基-2-丁烯 在 sodium hydride 作用下， 以 四氢呋喃 、 乙醚 、 mineral oil 为溶剂， 反应 3.26h， 生成 methyl Z-3-(diethylphosphoryloxy)-7-methyl-2,6-octadienoate
  参考文献：
  名称：

  Synthesis of Two Key Fragments of the Complex Polyhalogenated Marine Meroterpenoid Azamerone

  摘要：

  A concise route toward two advanced fragments in the context of the total synthesis of the unique natural product azamerone is reported. Key synthetic features include the enantioselective synthesis of an epoxysilane and its Lewis-acid-induced cyclization and the installation of the pyridazine ring via a formylation/condensation sequence. This route provides strategic insights into the chemistry of phthalazinediols, facilitating synthetic approaches toward this class of natural products.

  DOI：

  10.1021/acs.orglett.9b00090

文献信息

• Electrophilic cyclization of polyene allylsilanes. Synthesis of albicanyl acetate
  作者：Rosemary J. Armstrong、Francis L. Harris、Larry Weiler

  DOI：10.1139/v82-098

  日期：1982.3.1

  The allylsilanes 5 [Formula: see text] were prepared by a nickel(II) catalyzed coupling of trimethylsilylmethylmagnesium chloride with the enol phosphate of the corresponding β-keto esters. Stannic chloride and mercuric trifluoroacetate effected a cyclization of 5. The product from 5b was converted into the marine natural product, albicanyl acetate (1)[Formula: see text]

  联烯基硅烷5 [化学式：见文本] 是通过镍（II）催化的甲基三硅基甲烷镁和相应的β-酮酯的烯醇磷酸酯偶联制备的。氯化锡和三氟乙酸汞促进了5的环化反应。从5b得到的产物被转化成海洋天然产物阿尔比卡尼酯（1）[化学式：见文本]。
• Armstrong, Rosemary J.; Weiler, Larry, Canadian Journal of Chemistry, 1983, vol. 61, p. 2530 - 2539
  作者：Armstrong, Rosemary J.、Weiler, Larry

  DOI：——

  日期：——
• Mori, Kenji; Fujiwhara, Mitsuhiko, Liebigs Annalen der Chemie, 1989, p. 41 - 44
  作者：Mori, Kenji、Fujiwhara, Mitsuhiko

  DOI：——

  日期：——
• Synthesis of Two Key Fragments of the Complex Polyhalogenated Marine Meroterpenoid Azamerone
  作者：Simon D. Schnell、Anthony Linden、Karl Gademann

  DOI：10.1021/acs.orglett.9b00090

  日期：2019.2.15

  A concise route toward two advanced fragments in the context of the total synthesis of the unique natural product azamerone is reported. Key synthetic features include the enantioselective synthesis of an epoxysilane and its Lewis-acid-induced cyclization and the installation of the pyridazine ring via a formylation/condensation sequence. This route provides strategic insights into the chemistry of phthalazinediols, facilitating synthetic approaches toward this class of natural products.
• Enantioselective synthesis of both enantiomers of γ-ionone, γ-damascone, karahana lactone and karahana ether
  作者：Stephen Beszant、Elios Giannini、Giuseppe Zanoni、Giovanni Vidari

  DOI：10.1016/s0957-4166(02)00335-x

  日期：2002.7

  A straightforward enantioselective synthesis of both enantiomers of the title compounds is described starting from enantiopure methyl (2S,6R)- or (2R,6S)-cis-2-hydroxy-gamma-cyclogeraniate. These versatile building blocks are obtained by biomimetic cyclization of methyl (6S)- or (6R)-(Z)-6,7-epoxy-7-methyl-3-(trimethylsilyl)methyl-2-octenoate, respectively. The chiral information was encoded by a highly regioselective Sharpless asymmetric dihydroxylation of the corresponding diene. (C) 2002 Elsevier Science Ltd. All rights reserved.