(+/-)-(2R,6S)-2-methyl-1,7-dioxaspiro[5.5]undec-4-ene | 114047-59-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (+/-)-(2R,6S)-2-methyl-1,7-dioxaspiro[5.5]undec-4-ene
• 英文别名: 2-methyl-1,7-dioxaspiro<5.5>undec-4-ene；(2S,6R)-2-methyl-1,7-dioxaspiro[5.5]undec-4-ene
• CAS: 114047-59-5；132789-37-8；144480-97-7
• 化学式: C₁₀H₁₆O₂
• 分子量: 168.236
• InChiKey: UBRKXVAPUGPPAA-VHSXEESVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (+/-)-(2R,6S)-2-methyl-1,7-dioxaspiro[5.5]undec-4-ene 在 4-二甲氨基吡啶 、 potassium superoxide 、 N-溴代丁二酰亚胺(NBS) 、 18-冠醚-6 、 potassium carbonate 、 三乙胺 作用下， 以 四氢呋喃 、 四氯化碳 、 二氯甲烷 、 二甲基亚砜 为溶剂， 反应 6.0h， 生成 [(2R,3R,6S)-2-methyl-1,7-dioxaspiro[5.5]undec-4-en-3-yl] acetate
  参考文献：
  名称：

  Allylic functionalization of the 1,7-dioxaspiro[5.5]-undec-4-ene and d1,6,8-trioxadispiro[4.1.5.3]-pentadec-13-ene ring systems.

  摘要：

  Allylic bromination of the bicyclic spiroacetals 5, 6 and 7 gave predominantly the axial bromides 15, 21 and 23 which underwent S(N)2 displacement to the equatorial alcohols 17, 22 and 25 respectively, using potassium superoxide and 18-crown-6 in THF/DMSO (10:1). Allylic bromination of the cis-bis-spiroacetal 26 gave predominantly the rearranged allylic bromide 29 which afforded alcohols 30 and 31 resulting from both S(N)2' and S(N)2 displacement upon treatment with potassium superoxide. Bromination of the trans-bis-spiroacetal 27 afforded a complex mixture from which only the non-rearranged bromide 34 could be isolated. This bromide 34 afforded the axial alcohol 37 upon treatment with potassium superoxide.

  DOI：

  10.1016/s0040-4020(01)88235-1
• 作为产物：
  描述：

  在 碘 、 4-甲基苯磺酸吡啶 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 24.0h， 生成 (+/-)-(2R,6S)-2-methyl-1,7-dioxaspiro[5.5]undec-4-ene
  参考文献：
  名称：

  通过金属化的烯丙醇醚合成1,7-二氧杂螺环[5.5]十一碳-4-烯的新方法。他拉霉素A和B的正式合成

  摘要：

  经由相应的锂衍生物对甲氧基丙二烯进行顺序二烷基化，得到1,3-二烷基化的甲氧基丙二烯，其经酸催化的闭环反应成1,7-二氧杂螺并[5.5]十一烷基-4-烯；通过这种途径，已经制备了（6 S *，9 S *）-9-乙基-1,7-二恶唑螺[5.5]十一碳-4-烯（15b），其先前已被转化为他洛霉素A和B。

  DOI：

  10.1039/c39870000906

文献信息

• Allenol Ether Intermediates in the Synthesis of 1,7-Dioxaspiro[5.5]undec-4-enes and 1,6-Dioxaspiro[4.5]dec-3-enes
  作者：Philip Kocieński、Richard Whitby

  DOI：10.1055/s-1991-26640

  日期：——

  Sequential dialkylation of methoxyallene via the corresponding lithium derivatives gives 1,3-dialkylated methoxyallenes which undergo acid-catalysed ring closure to 1,7-dioxaspiro[5.5]undec-4-enes. Similarly, cyclic allenol ethers (2-vinylidenetetrahydropyrans) generated by rearrangement of 2-alkynyltetrahydropyrans cyclise on treatment with acid to give 1, 6-dioxaspiro[4.5]dec-3-enes.

  通过相应的锂衍生物对甲氧基阿伦烯进行序列二烷基化，得到的1,3-二烷基化甲氧基阿伦烯在酸性催化下发生环合反应，生成1,7-二氧杂螺[5.5]十一碳-4-烯。类似地，由2-炔基四氢吡喃重排生成的环状丙三烯醇醚（2-乙烯基四氢吡喃）在酸性处理下发生环合反应，生成1,6-二氧杂螺[4.5]癸-3-烯。
• Palladium mediated spiroketal synthesis: application to pheromone synthesis
  作者：Jeremy C. Conway、Peter Quayle、Andrew C. Regan、Christopher J. Urch

  DOI：10.1016/j.tet.2005.09.055

  日期：2005.12

  Stereospecific Stille coupling reactions of 2-metallo-dihydropyrans with Z-vinyl iodo alcohols and subsequent cyclisation provides rapid access to 1,7-dioxaspiro[5.5]undecane family of spiroketals.

  2-金属二氢吡喃与Z-乙烯基碘醇的立体特异性Stille偶联反应及随后的环化作用可快速获得1,7-二氧杂螺[5.5]十一烷螺环家族。
• Allylic oxidation of unsaturated spiroketals.
  作者：Margaret A Brimble、Michael K Edmonds、Geoffrey M Williams

  DOI：10.1016/s0040-4039(00)88531-7

  日期：1990.1

  Allylic bromination of the bicyclic spiroketals (4a-c) gave predominantly the axial bromides (6), (9) and (12) which underwent S(N)2 displacement to the equatorial alcohols (7), (11) and (14) respectively using KO2/18-crown-6 in THF/DMSO (10:1).
• Highly stereoselective syn-hydroxylation of spiroketals
  作者：Margaret A. Brimble、Michael R. Nairn、Yinqiu Wu

  DOI：10.1016/0040-4039(91)80625-g

  日期：1991.8

  The highly stereoselective syn-hydroxylation of unsaturated spiroketals (3,5) is reported.
• Kinetic resolution in the asymmetric dihydroxylation of 1,7-dioxaspiro[5.5]under-4-enes
  作者：Margaret A. Brimble、Andrew D. Johnston

  DOI：10.1016/s0957-4166(97)00152-3

  日期：1997.5

  The asymmetric dihydroxylation of unsaturated spiroacetals 1, 2, 3 was effected using the cinchona alkaloid ligands (DHQ)(2)-PHAL, (DHQD)(2)-PHAL and DHQ-IND, DHQD-IND with OsO4, K3Fe(CN)(6) and methanesulfonamide. Kinetic resolution of the spiroacetals was achieved and the reactions were monitored by chiral gas chromatography. (C) 1997 Elsevier Science Ltd.