(R)-2-methoxycyclohexanone

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (R)-2-methoxycyclohexanone
• 英文别名: 2-methoxycyclohexanone；(2R)-2-methoxycyclohexan-1-one
• 化学式: C₇H₁₂O₂
• 分子量: 128.171
• InChiKey: JYJURPHZXCLFDX-SSDOTTSWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  9
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  2-甲氧基-2-环己烯-1-酮 在 glucose dehydrogenase 、 D-葡萄糖 、 old yellow isoenzyme 1 from Saccharomyces carlsbergensis 、 nicotinamide adenine dinucleotide 作用下， 反应 24.0h， 生成 (R)-2-methoxycyclohexanone
  参考文献：
  名称：

  使用烯酸还原酶不对称合成 O-保护的丙烯酰基：通过保护基团修饰进行立体化学控制

  摘要：

  通过使用来自“老黄酶”家族的 11 种不同烯酸还原酶对 α,β-不饱和烷氧基酮进行不对称生物还原，以非外消旋形式获得 O-保护的环状 acyloins。生物转化的立体化学结果可以通过 O-保护基团的变化或底物的环大小来切换，这允许以高达 97% ee 的比例获得两种立体异构体，而 α-烷氧基烯酮很容易被接受为底物， β-类似物未转化。总的来说，α-烷氧基烯酮代表了一种新型的黄素依赖性烯还原酶底物。

  DOI：

  10.1002/ejoc.201001042

文献信息

• Flexible Stereoselective Functionalizations of Ketones through Umpolung with Hypervalent Iodine Reagents
  作者：Pushpak Mizar、Thomas Wirth

  DOI：10.1002/anie.201400405

  日期：2014.6.2

  The functionalization of carbonyl compounds in the α‐position has gathered much attention as a synthetic route because of the wide biological importance of such products. Through polarity reversal, or “umpolung”, we show here that typical nucleophiles, such as oxygen, nitrogen, and even carbon nucleophiles, can be used for addition reactions after tethering them to enol ethers. Our findings allow novel

  由于此类产品具有广泛的生物学重要性，因此羰基化合物在α位上的功能化作为合成途径已引起广泛关注。通过极性反转或“极性”，我们在这里表明典型的亲核试剂，例如氧，氮，甚至碳亲核试剂，在将它们束缚到烯醇醚后，可以用于加成反应。我们的发现可以进行新颖的逆合成规划，并可以快速组装以前只能通过多步序列访问的结构。
• Asymmetric Bioreduction of Alkenes Using Ene–Reductases YersER and KYE1 and Effects of Organic Solvents
  作者：Yanto Yanto、Christoph K. Winkler、Stephanie Lohr、Mélanie Hall、Kurt Faber、Andreas S. Bommarius

  DOI：10.1021/ol200394p

  日期：2011.5.20

  activated alkenes by KYE1 from Kluyveromyces lactis and Yers-ER from Yersinia bercovieri, two ene–reductases from the Old Yellow Enzyme family, showed a broad substrate spectrum with a moderate to excellent degree of stereoselectivity. Both substrate- and enzyme-based stereocontrols were observed to furnish opposite stereoisomeric products. The effects of organic solvents on enzyme activity and stereoselectivity

  乳酸克鲁维酵母（Kluyveromyces lactis）的KYE1和伯氏耶尔森氏菌（Yersinia bercovieri）的耶尔-ER（Yersinia bercovieri）的耶尔-ER（Kye1）的不对称反式生物还原，显示了较宽的底物谱，具有中等至极好的立体选择性。观察到基于底物和基于酶的立体对照均提供相反的立体异构产物。这项研究概述了有机溶剂对酶活性和立体选择性的影响，其中显示了即使在高有机溶剂含量下，两相系统己烷和甲苯也能维持生物还原效率。
• Synthesis of ruthenium-hydride complexes and preparation procedures of chiral alcohols and ketones
  申请人：Nagoya Industrial Science Research Institute

  公开号：US06720439B1

  公开（公告）日：2004-04-13

  trans-RuH(&eegr;1-BH4)[(S)-xylbinap][(S,S)-dpen] (0.00125 mmol), acetophenone (5.0 mmol), and 2-propanol (2.5 mL) were placed in an autoclave, and the resulting solution was repeatedly subject 5 times to a procedure of performing pressure reduction and argon introduction while stirring the solution for deaeration. A hydrogen tank was then connected to the autoclave, and after replacing the air inside an introduction tube with hydrogen, the pressure inside the autoclave was adjusted to 5 atmospheres and then hydrogen was released until the pressure dropped to 1 atmosphere. After repeating this procedure 10 times, the hydrogen pressure was adjusted to 8 atmospheres and stirring at 25° C. was performed for 12 hours. By concentrating the solution obtained by depressurization and subjecting the crude product to simple distillation, (R)-1-phenylethanol (yield: 95%) in the form of a colorless oily substance was obtained at an ee of 99%.

  (RuH(&eegr;1-BH4)[(S)-xylbinap][(S,S)-dpen]（0.00125 mmol）、苯乙酮（5.0 mmol）和2-丙醇（2.5 mL）被放入高压釜中，然后将得到的溶液在搅拌的同时进行5次压力减少和氩气引入的程序。然后将氢气罐连接到高压釜，并在用氢气替换引入管道内的空气后，调整高压釜内的压力至5大气压，然后释放氢气直至压力降至1大气压。重复此程序10次后，将氢气压力调整至8大气压，同时在25°C下搅拌12小时。通过浓缩减压得到的溶液，并将粗产品进行简单蒸馏，得到了（R）-1-苯乙醇（收率：95%），呈现为无色油状物质，其对映体纯度为99%。
• <i>trans</i>-RuH(η-BH₄)(binap)(1,2-diamine):  A Catalyst for Asymmetric Hydrogenation of Simple Ketones under Base-Free Conditions
  作者：Takeshi Ohkuma、Masatoshi Koizumi、Kilian Muñiz、Gerhard Hilt、Chizuko Kabuto、Ryoji Noyori

  DOI：10.1021/ja026136+

  日期：2002.6.1

  of a chiral RuCl2(diphosphine)(1,2-diamine) complex and NaBH4 forms trans-RuH(eta1-BH4)(diphosphine)(1,2-diamine) quantitatively. The TolBINAP/DPEN Ru complex has been characterized by single crystal X-ray analysis as well as NMR and IR spectra. The new Ru complexes allow for asymmetric hydrogenation of simple ketones in 2-propanol without an additional strong base. Various base-sensitive ketones are

  手性 RuCl2(diphosphine)(1,2-diamine) 络合物与 NaBH4 的反应定量地形成反式 RuH(eta1-BH4)(diphosphine)(1,2-diamine)。TolBINAP/DPEN Ru 复合物已通过单晶 X 射线分析以及核磁共振和红外光谱进行表征。新的 Ru 配合物允许在 2-丙醇中不对称氢化简单的酮，而无需额外的强碱。各种碱敏感性酮可在温和条件下转化为高对映体纯度的手性醇，底物/催化剂比高达 100 000。构型不稳定的 2-异丙基和 2-甲氧基环己酮可以通过高对映异构体区分进行动力学拆分。该程序克服了使用 RuCl2(diphosphine)(diamine) 和碱性碱的早期方法的缺点，
• Microbially-aided preparation of (S)-2-Methoxycyclohexanone key intermediate in the synthesis of Sanfetrinem
  作者：Claudio Fuganti、Piero Grasselli、Monica Mendozza、Stefano Servi、Gioia Zucchi

  DOI：10.1016/s0040-4020(96)01152-0

  日期：1997.2

  (S) 2-Methoxycyclohexanone 1, useful intermediate in the synthesis of Sanfetrinem 2, is obtained from (S) alpha-benzylidene cyclohexanol 4, derived from the ketone 3 through a short sequence involving as key step yeast reduction of the carbonyl group. The (R) enantiomer of 1 is similarly accessible from the (R) enantiomer of 4 obtained either upon Candida lipolytica-mediated reduction of 3 or from (R,S)-4 by porcine pancreatic lipase catalyzed acetylation with vinyl acetate. Also the saturated carbinols 7 and 8, which accompany 4 in the microbial reduction of 3, are converted into 1 through unexceptional steps. Nocardia opaca, Pichia etchelsii and Mucor subtilissimus provide from 3 upon reduction (S)-configurated 4, 7 and 8 possessing moderate-high ee values. (C) 1997, Elsevier Science Ltd.