(1R,4S,6S)-6-<(tert-butyldimethylsilyl)oxy>bicyclo<2.2.2>octan-2-one | 177748-71-9

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (1R,4S,6S)-6-<(tert-butyldimethylsilyl)oxy>bicyclo<2.2.2>octan-2-one
• 英文别名: (1R,4S,6S)-6-((tert-butyldimethylsilyl)oxy)bicyclo<2.2.2>octan-2-one；(1R,4S,6S)-6-(tert-Butyldimethylsilyloxy)bicyclo[2.2.2]octan-2-one；(1R,4S,6S)-6-[tert-butyl(dimethyl)silyl]oxybicyclo[2.2.2]octan-2-one
• CAS: 177748-71-9
• 化学式: C₁₄H₂₆O₂Si
• 分子量: 254.445
• InChiKey: JWTPIPVXHYXIIE-MDZLAQPJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.77
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.93
• 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：

  (1R,4S,6S)-6-<(tert-butyldimethylsilyl)oxy>bicyclo<2.2.2>octan-2-one 在 吡啶 、 potassium tert-butylate 、 四氯化钛 、 三乙胺 、 乙酰氯 、 lithium bromide 、 zinc(II) chloride 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 为溶剂， 反应 58.5h， 生成 (1R,4S,6S)-6-acetoxy-3-vinylidenebicyclo[2.2.2]octan-2-one
  参考文献：
  名称：

  Neighboring Group Participation in a Regio- and Stereoselective Chlorination of a Bicyclo[2.2.2]octanone

  摘要：

  The zinc chloride-mediated acetylation of the optically active silyl enol ether 2a gave the beta-diketone 3a (48%) together with the regio- and stereoselectively chlorinated compound 4 (27%). The yield of 4 increased to 70% by starting from the O-acetyl derivative 2c. The chlorination most likely occurs via neighboring group participation by the endo acetoxy group.

  DOI：

  10.1021/jo9607370
• 作为产物：
  描述：

  (1R,4S,6S)-6-(tert-Butyl-dimethyl-silanyloxy)-2-trimethylsilanyloxy-bicyclo[2.2.2]oct-2-ene 在 咪唑 、 四氯化钛 、 乙酰氯 作用下， 以 乙醚 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 生成 (1R,4S,6S)-6-<(tert-butyldimethylsilyl)oxy>bicyclo<2.2.2>octan-2-one
  参考文献：
  名称：

  Neighboring Group Participation in a Regio- and Stereoselective Chlorination of a Bicyclo[2.2.2]octanone

  摘要：

  The zinc chloride-mediated acetylation of the optically active silyl enol ether 2a gave the beta-diketone 3a (48%) together with the regio- and stereoselectively chlorinated compound 4 (27%). The yield of 4 increased to 70% by starting from the O-acetyl derivative 2c. The chlorination most likely occurs via neighboring group participation by the endo acetoxy group.

  DOI：

  10.1021/jo9607370

文献信息

• Asymmetric Reduction of Ketones with Catecholborane Using 2,6-BODOL Complexes of Titanium(IV) as Catalysts
  作者：Ian Sarvary、Fredrik Almqvist、Torbjörn Frejd

  DOI：10.1002/1521-3765(20010518)7:10<2158::aid-chem2158>3.0.co;2-i

  日期：2001.5.18

  Reductions performed with Ti(IV) complexes of ligands based on bicyclo[2.2.2]octane diols 5 and 6 are effective catalysts in the reduction of prochiral ketones to optically active alcohols, with catecholborane as the reducing agent. Methyl ketones are favored and enantiomeric excesses (ee) of < or =98% have been achieved with acetophenone as the substrate. Several other substrates were tested, among

  使用基于双环 [2.2.2] 辛烷二醇 5 和 6 的配体的 Ti(IV) 配合物进行的还原是将前手性酮还原为旋光醇的有效催化剂，其中儿茶酚硼烷作为还原剂。甲基酮是有利的，并且使用苯乙酮作为底物已经实现了 < 或 = 98% 的对映体过量 (ee)。测试了其他几种底物，其中包括 2-辛酮，它产生 2-辛醇，含 87% ee。检查了该方法的更多细节，例如温度、溶剂组成、分子筛 (4A) 的量和儿茶酚硼烷质量，以及配体对酸的敏感性。NMR 光谱方法用于深入了解配体和 [Ti(OiPr)4] 之间形成的配合物。为预催化剂提出了二聚体结构。
• Synthesis of Optically Active <i>endo</i>,<i>endo</i> Bicyclo[2.2.2]octane-2,5-diol, Bicyclo[2.2.2]octane-2,5-dione, and Related Compounds
  作者：Fredrik Almqvist、Niklas Ekman、Torbjörn Frejd

  DOI：10.1021/jo9601167

  日期：1996.1.1

  5S)-bicyclo[2.2.2]octane-2,5-diol ((+)-12; 98% ee) and several selectively protected optically active intermediates useful for synthetic transformations were synthesized via a 1,2-carbonyl transposition route starting from the easily available optically active (1R,4S,6S)-6-hydroxybicyclo[2.2.2]octan-2-one ((-)-2). The synthetic route also allowed the preparation of optically active (1S,4S)-bicyclo[2.2.2]octane-2

  旋光活性C（2）对称（1S，2S，4S，5S）-双环[2.2.2]辛烷-2,5-二醇（（+）-12; 98％ee）和几种选择性保护的旋光中间体有用通过容易获得的旋光性（1R，4S，6S）-6-羟基双环[2.2.2] octan-2-one（（-）-2）开始的1,2-羰基转座途径合成用于合成转化的化合物。合成路线还允许制备旋光的（1S，4S）-双环[2.2.2]辛烷-2，5-二酮（（+）-14； 98％ee）。
• New Ligands for the Titanium(IV)-Induced Asymmetric Reduction of Ketones with Catecholborane
  作者：Fredrik Almqvist、Lillemor Torstensson、Anette Gudmundsson、Torbjörn Frejd

  DOI：10.1002/anie.199703761

  日期：1997.3.3
• Bicyclo[2.2.2]octane-derived chiral ligands—synthesis and application of BODOLs in the asymmetric reduction of acetophenone with catecholborane
  作者：Annika Friberg、Ian Sarvary、Ola F. Wendt、Torbjörn Frejd

  DOI：10.1016/j.tetasy.2008.07.006

  日期：2008.8

  An improved synthetic route to the bicyclo[2.2.2]octane-2,6-diol ligands (2,6-BODOLS) allowed an increased structural variation of the ligand side-arm. The addition of aromatic or vinylic Grignard reagents to hydroxyketone 1 was highly selective and ligands 3f-3I were isolated in 84-97% yield. The addition of alkyl Grignard reagents containing beta-hydrogens resulted in lower yields (13-71%) due to competing ketone reduction. A number of 2,5-BODOLs were synthesized using a similar methodology. The ligands, together with Ti(OiPr)(4), were tested in the asymmetric reduction of acetophenone with catecholborane (up to 98% ee). 1-Naphthyl-BODOL 3i was employed as an allylboration reagent to benzaldehyde together with Sc(OTf)(3), resulting in (1S)-1-phenyl-3-buten-1-ol in 80% ee. (C) 2008 Elsevier Ltd. All rights reserved.