(1R,2S,9S)-11-methyl-13-oxa-7,11-diazatricyclo[7.3.1.0^2,7]tridecane | 1075213-41-0

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: (1R,2S,9S)-11-methyl-13-oxa-7,11-diazatricyclo[7.3.1.0^2,7]tridecane
• 英文别名: (1R,2S,9S)-11-methyl-13-oxa-7,11-diazatricyclo[7.3.1.02,7]tridecane
• CAS: 1075213-41-0
• 化学式: C₁₁H₂₀N₂O
• 分子量: 196.293
• InChiKey: ILZBSUJXPXWVGB-GARJFASQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  14
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  15.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (1R,2S,9S)-11-methyl-13-oxa-7,11-diazatricyclo[7.3.1.0^2,7]tridecane 、 zinc diacetate 以 四氢呋喃 为溶剂， 以80%的产率得到[N,N'-(1R,2S,7R,9S,11S)-11-methyl-13-oxa-7,11-diazatricyclo[7.3.1.0(2,7)]tridecane]zinc diacetate
  参考文献：
  名称：

  Unexpected activity of novel 9-oxabispidine zinc complexes in lactide polymerization

  摘要：

  The zinc dichlorido and zinc diacetato complexes of the chiral tricyclic 9-oxabispidine (1R,2S,9S)-11-methyl-13-oxa-7,11-diazatricyclo [7 3 1 0(27)] tridecane were prepared and characterized by X-ray crystallography. The latter complex was found to catalyze the solvent-free polymerization of D,L-lacticle to give polylactide (C) 2010 Elsevier B V All rights reserved

  DOI：

  10.1016/j.inoche.2009.12.024
• 作为产物：
  描述：

  (1R,2S,5R)-2-(4-hydroxybutyl)-7-methyl-9-oxa-3,7-diazabicyclo[3.3.1]nonane 在 偶氮二甲酸二异丙酯 、 三苯基膦 作用下， 以 甲苯 为溶剂， 反应 24.0h， 以80%的产率得到(1R,2S,9S)-11-methyl-13-oxa-7,11-diazatricyclo[7.3.1.0^2,7]tridecane
  参考文献：
  名称：

  Enantioselective total synthesis of the tricyclic 9-oxabispidine (1R,2S,9S)-11-methyl-13-oxa-7,11-diazatricyclo[7.3.1.02,7]tridecane

  摘要：

  The enantiomerically pure tricyclic 9-oxabispidine (1R,2S,9S)-11-methyl-13-oxa-7,11-diazatricyclo[7.3.1.0(2.7) ]tridecane, a potential substitute for (+)-sparteine in asymmetric synthesis, was prepared in 7 steps and in 11% overall yield from a chiral epoxy alcohol and (S)-epichlorohydrin. The key intermediate was a bicyclic 9-oxabispidine with an appropriately functionalized, endo-oriented side chain. (C) 2008 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2008.08.002
• 作为试剂：
  描述：

  4-甲氧基-α-甲基苯甲醇 在 (1R,2S,9S)-11-methyl-13-oxa-7,11-diazatricyclo[7.3.1.0^2,7]tridecane 、 C₁₁H₂₀Br₂N₂OPd 、 氧气 、 caesium carbonate 作用下， 以 氯仿 为溶剂， 反应 19.2h， 以33%的产率得到(R)-1-(4-甲氧基苯基)乙醇
  参考文献：
  名称：

  A Flexible Route to Chiral 2-endo-Substituted 9-Oxabispidines and Their Application in the Enantioselective Oxidation of Secondary Alcohols

  摘要：

  A new and flexible route to enantiomerically pure bi- and tricyclic 9-oxabispidines has been developed with use of (1R,5S)-7-methyl-2-oxo-9-oxa-3,7-diazabicyclo[3.3.1]nonane-3-carboxylic acid tert-butyl ester as the common late-stage intermediate. The 9-oxabispidines synthesized were evaluated as the chiral ligands in the Pd(II)-catalyzed oxidative kinetic resolution of secondary alcohols giving good to excellent selectivity factors of up to 19.

  DOI：

  10.1021/jo802409x

文献信息

• Chiral 2-<i>endo</i>-Substituted 9-Oxabispidines: Novel Ligands for Enantioselective Copper(II)-Catalyzed Henry Reactions
  作者：Matthias Breuning、David Hein、Melanie Steiner、Viktoria H. Gessner、Carsten Strohmann

  DOI：10.1002/chem.200901789

  日期：2009.11.23

  The CuCl2 complex of the tricyclic 9‐oxabispidine, which carries an 2‐endo,N‐anellated piperidine ring, is an excellent catalyst for enantioselective Henry reactions giving the S‐configured β‐nitro alcohols in 91–98 % ee (13 examples). Surprisingly, the analogous copper complexes of the bicyclic 9‐oxabispidines delivered the enantiocomplementary R‐configured products in 33–57 % ee. The respective transition

  开发了一种适用于克级的灵活方法，用于手性2-内基取代的9-氧杂哌啶。关键中间体是顺式构型的6-氨基甲基吗啉-2-腈，是由（R）-3-氨基丙烷-1，2-二醇和2-氯丙烯腈制得的。2-内型取代基是由Grignard加成，环化，并引入外切体选择性还原，从而家具在19-59％的产率的对映体纯二和三环9- oxabispidines。氯化亚铜2复合物中的三环9 oxabispidine的，其携带一个2-内型，N-稠合哌啶环，是对映选择性亨利反应给出一种极好的催化剂小号在91–98％ee中配置的β-硝基醇 （13个示例）。出人意料的是，双环9-氧杂萘啶类似的铜络合物以33–57 ％ee的浓度提供了对映体互补的R构型产物 。讨论了各自的过渡状态。
• Thieme Chemistry Journal Awardees - Where Are They Now? Bridgehead Lithiated 9-Oxabispidines
  作者：Matthias Breuning、Melanie Steiner、David Hein、Christian Hörl、Philipp Maier

  DOI：10.1055/s-0029-1217999

  日期：2009.10

  Bi- and tricyclic 9-oxabispidines are smoothly deprotonated at -78 ˚C by s-BuLi at one of the bridgehead carbon atoms to give α-lithio ethers, which were trapped with electrophiles in good yields. Rearrangements to ring-contracted N,O-acetals occurred upon warming in the absence of an electrophile. The α-lithio ether intermediates are presumably stabilized by negative hyperconjugation.

  双环和三环 9-oxabispidines 在 -78 ËC 温度下通过桥头碳原子上的 s-BuLi 顺利地去质子化，得到δ-硫代醚，并以良好的产率与亲电剂阱在一起。在没有亲电剂的情况下，升温后会发生重排，生成环收缩的 N,O-乙醛。δ-硫醚中间体可能是通过负超共轭作用稳定下来的。