(+/-)-cis-2-(phenylthio)cyclohexan-1-ol | 14032-04-3

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: (+/-)-cis-2-(phenylthio)cyclohexan-1-ol
• 英文别名: cis-2-(phenylthio)cyclohexanol；(+/-)-cis-2-(phenylthio)-1-cyclohexanol；(1R,2S)-2-phenylsulfanylcyclohexan-1-ol
• CAS: 14032-04-3；35550-80-2；60789-44-8；69222-98-6；102917-46-4；113349-44-3；133576-46-2
• 化学式: C₁₂H₁₆OS
• 分子量: 208.324
• InChiKey: FLFDJSCCPRMYPE-NEPJUHHUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  45.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (+/-)-cis-2-(phenylthio)cyclohexan-1-ol 在 1,3-丙二硫醇 、 迭氮酸 、 三苯基膦 、 偶氮二甲酸二乙酯 作用下， 以 二氯甲烷 、 甲苯 、 苯 为溶剂， 反应 24.0h， 生成 (+)-1-[3,5-bis(trifluoromethyl)phenyl]-3-[(1S,2S)-2-(phenylsulfanyl)cyclohexyl]thiourea
  参考文献：
  名称：

  Enantiopure trans-1-amino-2-(arylsulfanyl)cyclohexanes: novel chiral motifs for ligands and organocatalysts

  摘要：

  In order to obtain the title compounds (1R,2R)-cyclohexane-1,2-diol was stereoselectively converted into cis-(1R,2S)-2-(arylsulfanyl)cyclohexanols and these products were submitted to the nucleophilic substitution via the Mitsunobu reaction (HN3, DEAD). Reduction of the isolated azides gave the desired trans-(1S,2S)-1-amino-2-(arylsulfanyl)cyclohexanes. The (1S,2S)-1-amino-2-(2-aminophenylsulfanyl)cyclohexanes thus prepared were reacted with 3,5-bis(trifluoromethyl)phenyl isothiocyanate to furnish the respective bis-thiourea compounds. An application of a derivative of this type as an organocatalyst (20 mol %) in the Baylis-Hillman reaction gave the respective product in up to 93% ee. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2011.09.015
• 作为产物：
  描述：

  2-氯环己酮 在 sodium hydroxide 、 sodium tetrahydroborate 、 sodium hydride 作用下， 以 甲醇 、 乙腈 为溶剂， 生成 (+/-)-cis-2-(phenylthio)cyclohexan-1-ol
  参考文献：
  名称：

  Crumbie,R.L. et al., Australian Journal of Chemistry, 1978, vol. 31, p. 1965 - 1980

  摘要：

  DOI：

文献信息

• Ring-forming reaction via regioselective intramolecular insertion by (phenylthio) carbene into α c-h bond of alkoxides
  作者：Toshiro Harada、Eiji Akiba、Kohji Tsujimoto、Akira Oku

  DOI：10.1016/s0040-4039(00)88936-4

  日期：1985.1

  ω-(Phenylthio)-ω-chloroalkyl acetates were allowed to react with MeLi (3.2 equiv) to give 2-(phenylthio) cycloalkanols which were produced by the regioselective intramolecular insertion by (phenylthio) carbenes.

  使ω-（苯硫基）-ω-氯代烷基乙酸酯与MeLi（3.2当量）反应，得到2-（苯硫基）环烷醇，其通过（苯硫基）卡宾通过区域选择性分子内插入而产生。
• Oxirane ring opening reactions with thiols catalyzed by lanthanide complexes
  作者：Angelos E. Vougioukas、Henri B. Kagan

  DOI：10.1016/s0040-4039(00)96865-5

  日期：1987.1
• Single Enantiomer Epoxides by Bromomandelation of Prochiral Alkenes
  作者：Douglass F. Taber、Jiang-lin Liang

  DOI：10.1021/jo061818r

  日期：2007.1.1

  A combination of mandelic acid and N-bromosuccinimide efficiently converts prochiral alkenes into a readily separable 1:1 mixture of the bromomandelates. The diastereomerically pure bromomandelates are then converted into a variety of enantiomerically pure products. Terminal alkenes are converted into enantiomerically pure epoxides. Cyclohexene is converted into enantiomerically pure cis-2-azidocyclohexanol and cis-2-phenylthiocyclohexanol.
• Novel C2-symmetric chiral ligands: enantioselective transformation of cyclic 1,2-diols into 1,2-bis(phenylsulfenyl) and 1,2-bis(phenylselenyl) derivatives
  作者：Elżbieta Wojaczyńska、Jacek Skarżewski

  DOI：10.1016/j.tetasy.2008.02.001

  日期：2008.3

  Chiral C-2-symmetric S,S- and Se,Se-donating ligands as well as the C-1 mixed S,Se-donating ligands were prepared from optically active 1,2-cyclohexanediol and 1,2-cyclopentanediol via the respective S(N)2 reactions. The bis(chalcogen) ligands obtained effectively catalyze the asymmetric allylic alkylation with enantioselectivities of up to 50% ee. (C) 2008 Elsevier Ltd. All rights reserved.
• Chemoselective screening for the reduction of a chiral functionalised (±)-2-(phenylthio)cyclohexanone by whole cells of Brazilian micro-organisms
  作者：Leandro Piovan、Edna Kagohara、Luis C. Ricci、Artur F. Keppler、Marina Capelari、Leandro H. Andrade、João V. Comasseto、André L.M. Porto

  DOI：10.1016/j.tetasy.2008.10.003

  日期：2008.10

  The use of whole cells of micro-organisms to bring about the biotransformation of an organic compound offers a number of advantages, but problems caused by enzymatic Promiscuity may be encountered upon With Substrates hearing more than one functional group. A one-pot screening method, in which whole fungal cells were incubated with a Mixture of 4-rnethylcyclohexanone I and phenyl methyl Sulfide 2, has been employed to determine the chemoselectivity of various biocatalysts. The hyphomycetes, Aspergillus terreus CCT 3320 and A. terreus URM 3571, catalysed the oxidation of 2 accompanied by the reduction of I to 4-methylcyclohexanol 1a and, for strain A. terreus CCT 3320, the Baeyer-Villiger oxidation of 1. The Basidomycetes, Trametes versicolor CCB 202, Pycnoporus sanguineus CCB 501 and Trichaptum byssogenum CCB 203, catalysed the oxidation of 2 and the reduction 1, but no Baeyer-Villiger reaction products were detected. In contrast. Trametes rigida CCB 285 catalysed the biotransformation of 1 to 1a, exclusively, in the absence of any detectable Sulfide oxidation reactions. The chemoselective reduction Of (+/-)-2-(phenylthio)cyclohexanone 3 by T. rigida CCB 285 afforded exclusively the (+)-cis-(1R,2S) and (+)-trans-(1S,2S) diastereoisomers of 2-(phenylthio)cyclohexan-1-ol 3a in moderate yields (13% and 27%, respectively) and high enantiomeric excesses (>98%). Chemoselective screening for the reduction of a ketone and/or the oxidation Of a Sulfide group in one pot by whole cells of micro-organisms represents an attractive technique with applications in the development of synthesis of complex molecule hearing different functional groups. (C) 2008 Published by Elsevier Ltd.