(R)-2-cyclohexenyl acetate

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (R)-2-cyclohexenyl acetate
• 英文别名: (R)-3-acetoxy-1-cyclohexene；[(1R)-cyclohex-2-en-1-yl] acetate
• 化学式: C₈H₁₂O₂
• 分子量: 140.182
• InChiKey: MQNAWGURFBPDMW-QMMMGPOBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  10
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.62
• 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：

  (R)-2-cyclohexenyl acetate 在 palladium on activated charcoal 盐酸 、 sodium hydroxide 、 氯化亚砜 、 sodium azide 、 氢气 、 sodium hydride 、 三乙胺 、 硝苯酚 作用下， 以 甲醇 、 乙醇 、 二氯甲烷 、 丙酮 、 甲苯 、 苯 为溶剂， 反应 68.0h， 生成 (3aR,12R,12aR,12bS)-12-amino-2,3,3a,4,11,12,12a,12b-octahydro-10-hydroxyisoquino<2,1,8-lma>carbazol-5(1H)-one hydrochloride
  参考文献：
  名称：

  Synthesis of an enantiomerically pure aminoisoquinocarbazole with antiarrhythmic activity via lipase-catalyzed enantioselective transesterification

  摘要：

  Enantiomerically pure (R)-2-cydohexen-1-ol 5 was prepared via lipase-catalyzed enantioselective transesterification of 2-substituted cyclohexanol, and stereospecifically converted to (-)-(2-cyclohexenyl)acetic acid 4. Enantiomerically pure aminoisoquinocarbazole 1 (RS-2135) was synthesized stereoselectively from 4, using an intramolecular Dids-Alder reaction and Curtius rearrangement. Copyright (C) 1996 Elsevier Science Ltd

  DOI：

  10.1016/0957-4166(96)00199-1
• 作为产物：
  描述：

  2-溴环己酮 在 sodium tetrahydroborate 、 Burkholderia cepacia Amano PS lipase 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 甲醇 、 甲基叔丁基醚 为溶剂， 反应 30.0h， 生成 (R)-2-cyclohexenyl acetate
  参考文献：
  名称：

  Enzymatic preparation of (1S,2R)- and (1R,2S)-stereoisomers of 2-halocycloalkanols

  摘要：

  The stereoisomers of cis-2-halocycloalkanols were resolved by a kinetically controlled transesterification with vinyl acetate in the presence of lipases in organic media. High enantioselectivities (ee >98%) and good isolated yields were obtained for all substrates using the appropriate lipase. Burkholderia cepacia lipase was the most efficient enzyme for the resolution of these substrates. The enantiomeric purities of the compounds were defined by derivatization with Mosher's acid and the absolute configurations were determined by chemical correlation. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2012.11.011

文献信息

• Highly Enantioselective Synthesis of 3-Substituted Furanones by Palladium-Catalyzed Kinetic Resolution of Unsymmetrical Allyl Acetates
  作者：Bin Mao、Yining Ji、Martín Fañanás-Mastral、Giuseppe Caroli、Auke Meetsma、Ben L. Feringa

  DOI：10.1002/anie.201109075

  日期：2012.3.26

  near‐perfect Pd‐catalyzed kinetic resolution of 1,3‐disubstituted unsymmetrical allylic acetates uses silyl enol ethers as nucleophiles to access the important 3‐substituted‐furanone scaffold (see scheme; DACH=diaminocyclohexyl, dba=dibenzylideneacetone). The reaction proceeds under mild conditions and provides the desired products with excellent chemo‐, regio‐, and enantioselectivity.

  解决问题：1,3-二取代的不对称烯丙基乙酸酯的Pd催化动力学拆分接近完美，使用甲硅烷基烯醇醚作为亲核试剂来访问重要的3-取代的呋喃酮骨架（请参见方案; DACH =二氨基环己基，dba =二苄叉基丙酮） 。反应在温和的条件下进行，可提供具有优异的化学，区域和对映选择性的所需产物。
• Enzymatic resolution of stereoisomers of 2-iodocyclohexanol
  作者：O. O. Kolodiazhna、A. O. Kolodiazhna、O. I. Kolodiazhnyi

  DOI：10.1007/s11172-012-0305-1

  日期：2012.11

  All four optically active stereoisomers of 2-iodocyclohexanol were synthesized. Their enantiomeric purity was determined upon derivatization with Mosher’s acid, absolute configuration have been established by chemical correlation.

  合成了2-碘环己醇的全部四种具有光学活性的立体异构体，其对映体纯度通过与茅氏酸衍生物化反应测定，并通过化学关联确定了绝对构型。
• Discovery and Design of Family VIII Carboxylesterases as Highly Efficient Acyltransferases
  作者：Henrik Müller、Simon P. Godehard、Gottfried J. Palm、Leona Berndt、Christoffel P. S. Badenhorst、Ann‐Kristin Becker、Michael Lammers、Uwe T. Bornscheuer

  DOI：10.1002/anie.202014169

  日期：2021.1.25

  water, which enabled the synthesis of the drug moclobemide from methyl 4‐chlorobenzoate and 4‐(2‐aminoethyl)morpholine (ca. 20 % conversion). We solved the crystal structure of EstCE1 and detailed structure–function analysis revealed a three‐amino acid motif important for promiscuous acyltransferase activity. Introducing this motif into an esterase without acetyltransferase activity transformed a “hydrolase”

  混杂的酰基转移酶活性是某些水解酶优先催化酰基转移而不是水解的能力，即使在大量水中也是如此。然而，对映选择性差、转移效率低、产物水解显着以及底物范围有限等缺点使其应用存在相当大的缺陷。通过对几种水解酶进行基于活性的筛选，我们鉴定出第八家族羧酸酯酶 EstCE1 是一种前所未有的高效酰基转移酶。EstCE1 催化水中胺的不可逆酰胺化和氨甲酰化，从而能够从 4-氯苯甲酸甲酯和 4-(2-氨基乙基)吗啉合成药物吗氯贝胺（转化率约 20%）。我们解析了 EstCE1 的晶体结构，详细的结构功能分析揭示了一个对混杂酰基转移酶活性很重要的三氨基酸基序。将该基序引入没有乙酰转移酶活性的酯酶中，将“水解酶”转化为“酰基转移酶”。
• Enzyme- and Ruthenium-Catalyzed Dynamic Kinetic Resolution of Functionalized Cyclic Allylic Alcohols
  作者：Richard Lihammar、Renaud Millet、Jan-E. Bäckvall

  DOI：10.1021/jo402086z

  日期：2013.12.6

  Enantioselective synthesis of functionalized cyclic allylic alcohols via dynamic kinetic resolution has been developed. Cyclopentadienylruthenium catalysts were used for the racemization, and lipase PS-IM or CALB was employed for the resolution. By optimization of the reaction conditions the formation of the enone byproduct was minimized, making it possible to prepare a range of optically active functionalized

  已经开发了通过动态动力学拆分的功能化环状烯丙基醇的对映选择性合成。环戊二烯基钌催化剂用于消旋，脂肪酶PS-IM或CALB用于拆分。通过优化反应条件，将烯酮副产物的形成减至最少，从而有可能以良好的收率和较高的ee值制备一系列光学活性的官能化烯丙基醇。
• Indolobenzoquinoline derivatives, their preparation and their use as anti-arrhythmic drugs
  申请人：Sankyo Company Limited

  公开号：EP0415776A2

  公开（公告）日：1991-03-06

  Optically active compounds of formula (I): in which R1 is hydrogen or alkyl; Xb and Yb are hydrogen or hydroxy; and Z is -NRaRb in which Ra and Rb are hydrogen, alkyl or hydroxyalkyl, or a cyclic amino group; and pharmaceutically acceptable salts thereof have enhanced anti-arrhythmic activity and may be prepared by a stereospecific synthesis process.

  式(I)中的光学活性化合物：其中R1为氢或烷基；Xb和Yb为氢或羟基；Z为-NRaRb，其中Ra和Rb为氢、烷基或羟基烷基，或环状氨基；以及其药学上可接受的盐具有增强的抗心律失常活性，并可通过立体特异性合成过程制备。