(E)-3-Methoxymethoxy-11-methyl-13-oxa-bicyclo[8.2.1]trideca-1(12),4,10-triene | 136920-01-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 杂芳族化合物
• 英文名称: (E)-3-Methoxymethoxy-11-methyl-13-oxa-bicyclo[8.2.1]trideca-1(12),4,10-triene
• 英文别名: (4E)-3-(methoxymethoxy)-11-methyl-13-oxabicyclo[8.2.1]trideca-1(12),4,10-triene
• CAS: 136920-01-9
• 化学式: C₁₅H₂₂O₃
• 分子量: 250.338
• InChiKey: SDRSFTOWEYDHAW-FNORWQNLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  31.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (E)-3-Methoxymethoxy-11-methyl-13-oxa-bicyclo[8.2.1]trideca-1(12),4,10-triene 在 air 作用下， 以 乙酸乙酯 为溶剂， 反应 168.0h， 以47%的产率得到(2Z,7E)-6-Methoxymethoxy-2-methyl-cyclododeca-2,7-diene-1,4-dione
  参考文献：
  名称：

  Total Synthesis of the Pseudopterane (−)-Kallolide B, the Enantiomer of Natural (+)-Kallolide B

  摘要：

  A total synthesis of the enantiomer 35 of kallolide B was achieved starting from (S)-(-)-perillyl alcohol (8). Oxidative cleavage to the ester aldehyde 11 was effected by treatment of the epoxide 9 with H5IO6 followed by CH2N2. The allenyl ketone 13, obtained by SnCl2-promoted addition of 1-bromo-2-butyne to aldehyde 11 and subsequent Swern oxidation, cyclized to the furan 14 in the presence of catalytic AgNO3. Homologation of the derived aldehyde 15 with CBr4-Ph(3)P followed by n-BuLi and CH2O led to the propargylic alcohol 17, Formylation of the furan 17 (s-BuLi, DMF) and then Still-Horner-Emmons homologation yielded the (Z)-conjugated ester 22. Conversion of the propargylic alcohol function to the chloride 23 and ester reduction (DIBAL-H) furnished the chloro alcohol 24, which formed the cyclic ether 25 upon treatment with NaH. Ether 25 underwent a highly diastereoselective [2,3]Wittig ring contraction to the propargylic alcohol 26. The derived mesylate 36 was converted to the allenic ester 37 with CO and TMSCH(2)CH(2)OH in the presence of Pd(PPh(3))(4). Ester 37 was isomerized to the diastereomer 39 with Ph(3)P in CH3CN. Ester cleavage with TBAF followed by cyclization of the acid intermediate with catalytic AgNO3 led to butenolide 35, identical to kallolide B according to comparison of NMR spectra, but of opposite optical rotation.

  DOI：

  10.1021/jo960798y
• 作为产物：
  描述：

  (E)-6-Methoxymethoxy-2-methyl-cyclododeca-2,3,7-trienone 在 silica gel 、 silver nitrate 作用下， 以 正己烷 为溶剂， 反应 3.5h， 以98%的产率得到(E)-3-Methoxymethoxy-11-methyl-13-oxa-bicyclo[8.2.1]trideca-1(12),4,10-triene
  参考文献：
  名称：

  Synthesis of Furans and 2,5-Dihydrofurans by Ag(I)-Catalyzed Isomerization of Allenones, Alkynyl Allylic Alcohols, and Allenylcarbinols

  摘要：

  DOI：

  10.1021/jo00123a040

文献信息

• Synthesis of macrocyclic homopropargylic alcohols through intramolecular SE' addition of allenylstannanes and their subsequent conversion to 2,5-furanocycles
  作者：James A. Marshall、Xiao Jun Wang

  DOI：10.1021/jo00022a008

  日期：1991.10

  The 2,5-furanocyclododecenes 16, 20, and 24 have been prepared by a new route involving intramolecular S(E)' addition of propargylic stannanes 3, 6, and 9 then exposure of the derived allenones 14, 19, and 23 to AgN-O3-CaCO3 in aqueous acetone at room temperature.
• Synthesis of 2,5-furanocycles through intraannular cyclization of macrocyclic allenones
  作者：James A. Marshall、Xiao Jun Wang

  DOI：10.1021/jo00038a029

  日期：1992.6

  A new approach to 2,5-bridged furanocyclic compounds was demonstrated for rings of 12-14 members. Accordingly, allenylstannyl aldehydes 1.16, 2.11, 3.12a, 3.12b, 4.12, 5.15, and 6.12, upon treatment with BF3.OEt2 at -78-degrees-C, smoothly cyclized to the homopropargylic alcohols 1.17, 2.12,3.13a, 3.13b, 4.13,5.16, and 6.13 in 87-94% yield. Oxidation and basic isomerization afforded the allenones 1.19, 2.14, 3.15a, 3.15b, 4.14, 5.18, and 6.15 in high yield. Intraannular cyclization to the furanocycles 1.21, 2.15, 3.16a, 3.16b, 4.16, 5.19, and 6.16 was effected with catalytic AgNO3 and CaCO3 in aqueous acetone. Furanocycles 1.21, 2.15, 3.16a, and 3.16b, with an appropriately disposed transannular (Z)-double bond, underwent facile intramolecular Diels-Alder cyclization in over 90% yield. The 12-membered furanocycles 4.16 and 5.19 with a transannular (E) double bond did not cyclize but instead were oxidized by the AgNO3 catalyst to macrocyclic enediones 4.17 and 5.20. These unusual furan reactions are presumably facilitated by ring strain (furan bending) in accord with molecular mechanics calculations.