S-ethyl (2S,3R,4E)-2-(t-butyldimethylsiloxy)-3-hydroxy-5-phenyl-4-pentenethioate | 138510-01-7

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂醇
• 英文名称: S-ethyl (2S,3R,4E)-2-(t-butyldimethylsiloxy)-3-hydroxy-5-phenyl-4-pentenethioate
• 英文别名: S-ethyl (E,2S,3R)-2-[tert-butyl(dimethyl)silyl]oxy-3-hydroxy-5-phenylpent-4-enethioate
• CAS: 138510-01-7
• 化学式: C₁₉H₃₀O₃SSi
• 分子量: 366.597
• InChiKey: VEUXBFJUKRSQCR-KGWAOHPJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.73
• 重原子数：
  24
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  71.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  叔丁基二甲基甲硅烷基氧基乙酰氯 在 吡啶 、 tin(II) trifluoromethanesulfonate 、 dibutyltin diacetate 、 (S)-1-Ethyl-2-<(piperidin-1-yl)methyl>pyrrolidine 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 30.0h， 生成 S-ethyl (2S,3R,4E)-2-(t-butyldimethylsiloxy)-3-hydroxy-5-phenyl-4-pentenethioate
  参考文献：
  名称：

  Diastereo- and Enantioselective Synthesis ofsyn- andanti-1,2-Diol Units by Asymmetric Aldol Reactions

  摘要：

  通过利用α-烷氧基硫代乙酸S-酯与醛的不对称缩醛反应，制备了反式和顺式1,2-二醇单元。在存在三氟甲磺酸锡（II）、手性二胺和二丁基二乙酸锡的情况下，（Z）-2-苄氧基-1-乙硫基-1-（三甲基硅氧基）乙烯与醛反应，以高收率生成具有优异非对映性和对映选择性相应的反式缩醛加合物，而顺式加合物则是在相同的反应条件下由（Z）-2-（叔丁基二甲基硅氧基）-1-乙硫基-1-（三甲基硅氧基）乙烯和醛生成的。因此，通过简单地选择硅醇醚烷氧基部分的保护基团，即可以优异的对映选择性合成两种非对映体。

  DOI：

  10.1246/bcsj.67.1708

文献信息

• Highly Enantioselective Synthesis of syn-α,β-Dihydroxy Thioesters by the Asymmetric Aldol Reaction Using a Chiral Tin(II) Lewis Acid
  作者：Teruaki Mukaiyama、Isamu Shiina、Shu Kobayashi

  DOI：10.1246/cl.1991.1901

  日期：1991.11

  syn-α,β-Dihydroxy thioesters are prepared in good yields with high diastereo- and enantioselectivities by the asymmetric aldol reaction of 1-trimethylsiloxy-1-ethylthio-2-t-butyldimethylsiloxyethene with aldehydes using a chiral promoter consisting of tin(II) triflate, a chiral diamine and dibutyltin diacetate.

  使用由锡 (II) 组成的手性促进剂，通过 1-三甲基甲硅烷氧基-1-乙硫基-2-叔丁基二甲基甲硅烷氧基乙烯与醛的不对称醛醇反应，以高产率和高非对映选择性和对映选择性制备了合成-α,β-二羟基硫酯三氟甲磺酸酯，一种手性二胺和二乙酸二丁基锡。
• Enantioselective synthesis of both diastereomers, including the α-alkoxy-β-hydroxy-β-methyl(phenyl) units, by chiral tin(II) Lewis acid-mediated
  作者：Shū Kobayashi、Mineko Horibe、Yumi Saito

  DOI：10.1016/s0040-4020(01)85531-9

  日期：——

  Diastereo- and enantioselective synthesis of both diastereomers, including the alpha-alkoxy-beta-hydroxy-beta-methyl(phenyl) units, was performed by using chiral tin(II) Lewis acid-mediated asymmetric aldol reactions of a-alkoxy silyl enol ethers with alpha-ketoesters. (S)-1-Propyl-2-[(1,2,3,4-tetrahydroisoquinolinyl))methyl]pyrrolidine (13), a new type of chiral diamine, was found to be effective as a chiral source in these reactions and also in the reactions of 2-(t-butyldimethylsiloxy)-1-ethylthio-1-(trimethylsiloxy)ethene (9) with aldehydes for the synthesis of optically active syn-a,p-dihydroxy thioester derivatives. (-)-2-C-Methyl-D-erythrono-1,4-lactone and (+)-2-C-methyl-L-threono-1,4-lactone were synthesized by using these reactions.
• Chiral Lewis Acid Controlled Synthesis (CLAC Synthesis): Chiral Lewis Acids Influence the Reaction Course in Asymmetric Aldol Reactions for the Synthesis of Enantiomeric Dihydroxythioester Derivatives in the Presence of Chiral Diamines Derived from L-Proline
  作者：Shū Kobayashi、Mineko Horibe

  DOI：10.1002/chem.19970030914

  日期：1997.9

  AbstractBoth enantiomers of 2,3‐dihy‐droxythioester derivatives were prepared with almost perfect stereochemical control by chiral Lewis acid controlled synthesis (CLAC synthesis). CLAC synthesis means synthesis of all individual diastereomers or enantiomers from the same starting materials by designing chiral Lewis acids. For example, (Z)‐1‐ethyl‐thio‐1‐(trimethylsiloxy)‐2‐(tert‐butyldi‐methylsiloxy)ethene (1) reacted with aldehydes in the presence of chiral tin(II) Lewis acids using (S)‐1‐methyl‐2‐[(isoin‐dolinyl)methyl]pyrrolidine (4) and (S)‐1‐methyl‐2‐[(indolinyl)methyl]pyrrolidine (5) to afford enantiomeric dihydroxy‐thioester derivatives. Chiral diamines 4 and 5, which were readily prepared from L‐proline, differ only in the fusion point of the benzene ring connected to the pyrrolidine moiety. The unique selectivities were ascribed to the conformational difference between the chiral tin(II) Lewis acids of chiral diamines 4 and 5, and the function of chiral sources for obtaining high selectivities has also been clarified.
• Mukaiyama Teruaki, Shiina Isamu, Uchiro Hiromi, Kobayashi Shue, Bull. Chem. Soc. Jap, 67 (1994) N 6, S 1708-1716
  作者：Mukaiyama Teruaki, Shiina Isamu, Uchiro Hiromi, Kobayashi Shue

  DOI：——

  日期：——
• Diastereo- and Enantioselective Synthesis of<i>syn</i>- and<i>anti</i>-1,2-Diol Units by Asymmetric Aldol Reactions
  作者：Teruaki Mukaiyama、Isamu Shiina、Hiromi Uchiro、Shu Kobayashi

  DOI：10.1246/bcsj.67.1708

  日期：1994.6

  syn- and anti-1,2-Diol units were prepared by using asymmetric aldol reactions of the silyl enol ethers derived from α-alkoxythioacetic S-esters with aldehydes. In the presence of tin(II) triflate, a chiral diamine, and dibutyltin diacetate, (Z)-2-benzyloxy-1-ethylthino-1-(trimethylsiloxy)ethene reacted with aldehydes to afford the corresponding anti-aldol adducts in high yields with excellent diastereo- and enantioselectivities, while syn-adducts were obtained from (Z)-2-(t-butyldimethylsiloxy)-1-ethylthio-1-(trimethylsiloxy)ethene and aldehydes under the same reaction conditions. Thus, both diastereomers can be synthesized in excellent enantiomeric excesses by simply choosing the protective groups of the alkoxyl parts of the silyl enol ethers.

  通过利用α-烷氧基硫代乙酸S-酯与醛的不对称缩醛反应，制备了反式和顺式1,2-二醇单元。在存在三氟甲磺酸锡（II）、手性二胺和二丁基二乙酸锡的情况下，（Z）-2-苄氧基-1-乙硫基-1-（三甲基硅氧基）乙烯与醛反应，以高收率生成具有优异非对映性和对映选择性相应的反式缩醛加合物，而顺式加合物则是在相同的反应条件下由（Z）-2-（叔丁基二甲基硅氧基）-1-乙硫基-1-（三甲基硅氧基）乙烯和醛生成的。因此，通过简单地选择硅醇醚烷氧基部分的保护基团，即可以优异的对映选择性合成两种非对映体。