(2R)-1-(Tosyloxy)decan-2-ol | 155721-05-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (2R)-1-(Tosyloxy)decan-2-ol
• 英文别名: (R)-2-hydroxydecyl tosylate；[(2R)-2-hydroxydecyl] 4-methylbenzenesulfonate
• CAS: 155721-05-4
• 化学式: C₁₇H₂₈O₄S
• 分子量: 328.473
• InChiKey: UHMUNXMEITYUKV-MRXNPFEDSA-N

物化性质

• 沸点：
  462.7±28.0 °C(Predicted)
• 密度：
  1.093±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  22
• 可旋转键数：
  11
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  72
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (2R)-1-(Tosyloxy)decan-2-ol 在 sodium hydroxide 、 硫酸 、 sodium ethanolate 、 potassium carbonate 作用下， 以 甲醇 为溶剂， 反应 13.0h， 生成 (R)-4-dodecanolide
  参考文献：
  名称：

  Ring opening of 2,3-epoxy 1-tosylates to halohydrins and subsequent elaboration to asymmetrical alcohols

  摘要：

  2,3-epoxy alcohols-1-tosylates are regio and chemoselectively opened to the corresponding 3-halohydrins (I, Br, Cl): the reduction of the iodohydrins to the monoprotected diols and subsequent standard coupling of the tosyl group leads to a straightforward synthesis of optically active naturally occurring pheromones.

  DOI：

  10.1016/s0040-4039(00)75820-5
• 作为产物：
  描述：

  1,2-癸二醇 在 吡啶 、 lipase PS from Burkholderia cepacia 、 二异丁基氢化铝 、 二正丁基氧化锡 、 三乙胺 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 、 aq. phosphate buffer 、 二氯甲烷 、 甲苯 为溶剂， 反应 70.0h， 生成 (2R)-1-(Tosyloxy)decan-2-ol
  参考文献：
  名称：

  Synthesis of optically active heterocyclic compounds via deracemization of 1,2-diol monotosylate derivatives bearing a long aliphatic chain by a combination of enzymatic hydrolysis with Mitsunobu inversion

  摘要：

  We have succeeded in accomplishing the deracemization of (+/-)-2-acetoxydecyl and (+/-)-acetoxy-6-benzyloxyhexyl tosylates, which have a long substituent, via an enzyme-mediated enantioselective hydrolysis with a Mitsunobu inversion using polymer-supported triphenylphosphine to afford the corresponding (S)-enantiomer. Enantiomerically pure (S)- and (R)-gamma-dodecalactones, a fruit flavor, were synthesized from (S)-2-acetoxydecyl tosylate as the mutual starting material. The poisonous alkaloid (S)-coniine was also synthesized using enantiomerically pure allyl amine as the key intermediate derived from (S)-acetoxy-6-benzyloxyhexyl tosylate. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2012.11.023

文献信息

• Enzyme-mediated enantioselective hydrolysis of 1,2-diol monotosylate derivatives bearing an unsaturated substituent
  作者：K. Matsumoto、K. Oohana、M. Hashimoto、K. Usuda、T. Shimoda、H. Ohshima、Y. Suzuki、T. Togawa

  DOI：10.1016/j.tet.2018.05.087

  日期：2018.7

  We have succeeded in the easy preparation of optically active 1,2-diol monotosylates bearing an unsaturated substituent via enzymatic hydrolysis. Lipase PS quickly catalyzes the hydrolyses of 2-acetoxybut-3-enyl tosylate, which has a double bond, and 2-acetoxybut-3-ynyl tosylate, which has a triple bond, with excellent enantioselectivity to afford the corresponding optically active compounds. The reaction

  我们已经成功地通过酶水解容易地制备了带有不饱和取代基的光学活性的1,2-二醇单甲苯磺酸酯。脂肪酶PS快速催化具有双键的2-乙酰氧基丁-3-烯基甲苯磺酸酯和具有三键的2-乙酰氧基丁-3-炔基甲苯磺酸酯的水解，具有出色的对映选择性，可提供相应的旋光化合物。该反应也适用于在末端具有双键的较长链的乙酸酯。为了证明该方法的适用性，已从外消旋的2-乙酰氧基戊-4-烯基甲苯磺酸酯中分几步合成了对映体纯的（R）-马苏阿内酯，一种天然椰子香精。此外，该酶可以识别烯烃的立体化学，而（Z）-烯基结构比（E）-异构体更适合于对映选择性水解。
• C-1 Reactivity of 2,3-Epoxy Alcohols via Oxirane Opening with Metal Halides: Applications and Synthesis of Naturally Occurring 2,3-Octanediol, Muricatacin, 3-Octanol, and 4-Dodecanolide
  作者：Carlo Bonini、Chiara Federici、Leucio Rossi、Giuliana Righi

  DOI：10.1021/jo00120a025

  日期：1995.7

  The C-1 reactivity of 2,3-epoxy alcohols and derivatives has been examined thoroughly. In the first approach a rearrangement opening of 2,3-epoxy alcohols with LiI leads to 1-iodo 2,3-diols with erythro or three stereochemistry starting from trans or cis epoxy alcohols. Subsequent coupling with a carbon nucleophile can lead to a series of vicinal diols with predicted relative and absolute stereochemistry: the described methodology has been applied to the asymmetric synthesis of the naturally occurring (S,S)-2,3-octanediol and (R,R)-muricatacin. The second approach, starting from easily available tosyloxy epoxides, leads to the highly regioselective opening of the oxirane ring with Li halides. The 3-iodohydrins obtained can be reduced to the corresponding 1-(tosyloxy)alkan-2-ols and then coupled with common carbon nucleophiles to afford, in high yields, optically active alcohols. This methodology has been applied to the asymmetric synthesis of naturally occurring pheromones like 3(R)-octanol and 4(R)-dodecanolide.
• Immobilization of lipase from Burkholderia cepacia into calcium carbonate microcapsule and its use for enzymatic reactions in organic and aqueous media
  作者：Masahiro Fujiwara、Kumi Shiokawa、Koji Yotsuya、Kazutsugu Matsumoto

  DOI：10.1016/j.molcatb.2014.08.009

  日期：2014.11

  We disclosed a useful procedure for the immobilization of a lipase from Burkholderia cepacia based on its encapsulation into vaterite calcium carbonate microcapsule. The immobilized enzyme had an adequate activity for the hydrolysis of 4-nitrophenyl acetate, which was preserved over 2 years in storage at 4 degrees C. The enantioselective esterification of (+/-)-1-phenylethanol with vinyl acetate using the immobilized lipase smoothly progressed to afford the corresponding optically active compounds, where the enzyme was easily recovered for reuse. Although the hydrolysis of (+/-)-2-acetoxyhexyl tosylate in aqueous solution was catalyzed by the enzyme, the phase transition of calcium carbonate from vaterite to poorly porous calcite during the reaction prevented the access of the reactant to the active site of the lipase, resulting in the significant decrease of the activity of the recovered enzyme. However, the treatment of the immobilized enzyme with zinc chloride solution inhibited the phase transition under the reaction conditions. The enzyme after the zinc treatment was recyclable for the hydrolysis of the substrate without significant decrease of the reactivity even after the uses in aqueous media. (C) 2014 Elsevier B.V. All rights reserved.
• Synthesis of optically active heterocyclic compounds via deracemization of 1,2-diol monotosylate derivatives bearing a long aliphatic chain by a combination of enzymatic hydrolysis with Mitsunobu inversion
  作者：Kazutsugu Matsumoto、Kazumasa Usuda、Hirokazu Okabe、Manabu Hashimoto、Yasutaka Shimada

  DOI：10.1016/j.tetasy.2012.11.023

  日期：2013.2

  We have succeeded in accomplishing the deracemization of (+/-)-2-acetoxydecyl and (+/-)-acetoxy-6-benzyloxyhexyl tosylates, which have a long substituent, via an enzyme-mediated enantioselective hydrolysis with a Mitsunobu inversion using polymer-supported triphenylphosphine to afford the corresponding (S)-enantiomer. Enantiomerically pure (S)- and (R)-gamma-dodecalactones, a fruit flavor, were synthesized from (S)-2-acetoxydecyl tosylate as the mutual starting material. The poisonous alkaloid (S)-coniine was also synthesized using enantiomerically pure allyl amine as the key intermediate derived from (S)-acetoxy-6-benzyloxyhexyl tosylate. (C) 2012 Elsevier Ltd. All rights reserved.
• Ring opening of 2,3-epoxy 1-tosylates to halohydrins and subsequent elaboration to asymmetrical alcohols
  作者：Chiara Federici、Giuliana Righi、Leucio Rossi、Carlo Bonini、Lucia Chiummiento、Maria Funicello

  DOI：10.1016/s0040-4039(00)75820-5

  日期：1994.1

  2,3-epoxy alcohols-1-tosylates are regio and chemoselectively opened to the corresponding 3-halohydrins (I, Br, Cl): the reduction of the iodohydrins to the monoprotected diols and subsequent standard coupling of the tosyl group leads to a straightforward synthesis of optically active naturally occurring pheromones.