ethyl (E)-3-trifluoromethanesulfonyloxy-2-hexenoate | 353744-11-3

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: ethyl (E)-3-trifluoromethanesulfonyloxy-2-hexenoate
• 英文别名: (E)-ethyl 3-(trifluoromethylsulfonyloxy)hex-2-enoate；ethyl (E)-3-(trifluoromethylsulfonyloxy)hex-2-enoate
• CAS: 353744-11-3
• 化学式: C₉H₁₃F₃O₅S
• 分子量: 290.26
• InChiKey: CXCDOJLVKIQRCP-VOTSOKGWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  18
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  78
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  ethyl (E)-3-trifluoromethanesulfonyloxy-2-hexenoate 在 四(三苯基膦)钯 、 Lactobacillus brevis alcohol dehydrogenase 、 Saccharomyces pastorianus old yellow enzyme, isoenzyme OYE₂ 、 烟酰胺腺嘌呤双核苷酸磷酸盐 、 异丙醇 、 sodium hydroxide 作用下， 以 甲醇 、 aq. phosphate buffer 、 N,N-二甲基甲酰胺 为溶剂， 反应 18.0h， 生成 (S)-3-cyanohexanoic acid
  参考文献：
  名称：

  Chemoenzymatic Asymmetric Synthesis of Pregabalin Precursors via Asymmetric Bioreduction of β-Cyanoacrylate Esters Using Ene-Reductases

  摘要：

  The asymmetric bioreduction of a library of beta-cyanoacrylate esters using ene-reductases was studied with the aim to provide a biocatalytic route to precursors for GABA analogues, such as pregabalin. The stereochemical outcome could be controlled by substrate-engineering through size-variation of the ester moiety and by employing stereochemically pure (E)- or (Z)-isomers, which allowed to access both enantiomers of each product in up to quantitative conversion in enantiomerically pure form. In addition, stereoselectivities and conversions could be improved by mutant variants of OPR1, and the utility of the system was demonstrated by preparative-scale applications.

  DOI：

  10.1021/jo302484p
• 作为产物：
  描述：

  2-戊酮 在 四甲基氢氧化铵 、 sodium hydride 作用下， 以 四氢呋喃 、 正庚烷 、 水 、 mineral oil 为溶剂， 反应 21.75h， 生成 ethyl (E)-3-trifluoromethanesulfonyloxy-2-hexenoate
  参考文献：
  名称：

  Chemoenzymatic Asymmetric Synthesis of Pregabalin Precursors via Asymmetric Bioreduction of β-Cyanoacrylate Esters Using Ene-Reductases

  摘要：

  The asymmetric bioreduction of a library of beta-cyanoacrylate esters using ene-reductases was studied with the aim to provide a biocatalytic route to precursors for GABA analogues, such as pregabalin. The stereochemical outcome could be controlled by substrate-engineering through size-variation of the ester moiety and by employing stereochemically pure (E)- or (Z)-isomers, which allowed to access both enantiomers of each product in up to quantitative conversion in enantiomerically pure form. In addition, stereoselectivities and conversions could be improved by mutant variants of OPR1, and the utility of the system was demonstrated by preparative-scale applications.

  DOI：

  10.1021/jo302484p

文献信息

• Stereocontrolled Synthesis of 13-Substituted Retinoic Acids by Palladium-Catalyzed Coupling Reaction of Alkenyl Stannane with Vinyl Triflate
  作者：Akimori Wada、Kouki Fukunaga、Masayoshi Ito

  DOI：10.1055/s-2001-14908

  日期：——

  A novel method for the stereoselective synthesis of all-E-, 13Z- and 9Z-retionic acid esters was developed by palladium-catalyzed cross coupling reactions of tetraenyl stannanes with E- or Z-vinyl triflates in good yields. Applying this methodology, 13-substituted all-E- and 9Z-retionic acids were prepared in satisfactory yields.

  一种新的立体选择性合成全E-、13Z-和9Z-维甲酸酯的方法，通过钯催化的四烯基锡与E型或Z型乙烯基三氟甲磺酸酯的交叉耦合反应，产率良好。应用此方法，成功以满意的产率制备了13-取代的全E-和9Z-维甲酸。
• Preparation and biological activity of 13-substituted retinoic acids
  作者：Akimori Wada、Kouki Fukunaga、Masayoshi Ito、Yukari Mizuguchi、Kimie Nakagawa、Toshio Okano

  DOI：10.1016/j.bmc.2004.04.047

  日期：2004.7

  13-Demethyl or 13-substituted all-E- and 9Z-retinoic acids were synthesized using a palladium-catalyzed coupling reaction of enol triflates and tributylstannylolefins. Their biological activities were then measured. The 13-ethyl analogs exhibited approximately one-half of the antiproliferative and differentiation-inducing activity of ATRA in HL-60 cells. In contrast, in the 9Z-derivatives, all analogs, except for the 13-butyl derivatives, showed apoptosis-inducing activity. (C) 2004 Elsevier Ltd. All rights reserved.
• Chemoenzymatic Asymmetric Synthesis of Pregabalin Precursors via Asymmetric Bioreduction of β-Cyanoacrylate Esters Using Ene-Reductases
  作者：Christoph K. Winkler、Dorina Clay、Simon Davies、Pat O’Neill、Paul McDaid、Sebastien Debarge、Jeremy Steflik、Mike Karmilowicz、John W. Wong、Kurt Faber

  DOI：10.1021/jo302484p

  日期：2013.2.15

  The asymmetric bioreduction of a library of beta-cyanoacrylate esters using ene-reductases was studied with the aim to provide a biocatalytic route to precursors for GABA analogues, such as pregabalin. The stereochemical outcome could be controlled by substrate-engineering through size-variation of the ester moiety and by employing stereochemically pure (E)- or (Z)-isomers, which allowed to access both enantiomers of each product in up to quantitative conversion in enantiomerically pure form. In addition, stereoselectivities and conversions could be improved by mutant variants of OPR1, and the utility of the system was demonstrated by preparative-scale applications.