methyl (2E,5S)-5-{[tert-butyl(dimethyl)silyl]oxy}-2-hexenoate | 133522-08-4

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: methyl (2E,5S)-5-{[tert-butyl(dimethyl)silyl]oxy}-2-hexenoate
• 英文别名: Methyl (S,E)-5-tert-Butyldimethylsilyoxyhex-2-enoate；methyl (2E,5S)-5-t-butyldimethylsiloxy-2-hexenoate；methyl (E,5S)-5-[tert-butyl(dimethyl)silyl]oxyhex-2-enoate
• CAS: 133522-08-4
• 化学式: C₁₃H₂₆O₃Si
• 分子量: 258.433
• InChiKey: JZACRADDHGBASF-UQSGXBNBSA-N

物化性质

• 沸点：
  282.4±23.0 °C(Predicted)
• 密度：
  0.914±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.52
• 重原子数：
  17
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.77
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl (2E,5S)-5-{[tert-butyl(dimethyl)silyl]oxy}-2-hexenoate 在 4-二甲氨基吡啶 、 sodium hydroxide 、 三氯化铝 、 2,4,6-三氯苯甲酰氯 、 D(+)-10-樟脑磺酸 、 水 、 sodium acetate 、 溶剂黄146 、 三乙胺 、 N,N'-二环己基碳二亚胺 、 锌 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 xylene 为溶剂， 反应 54.5h， 生成 (+)-macrosphelide G
  参考文献：
  名称：

  New total syntheses of (+)-macrosphelides C, F and G

  摘要：

  The total synthesis of (+)-macrosphelide C 1 (25% overall yield in nine steps), (+)-macrosphelide F 2 (20% overall yield in nine steps) and (+)-macrosphelide G 3 (22% overall yield in nine steps) has been achieved from the chemoenzymatic reaction product (4R,5S)-4-benyloxy-5-hydroxy-(2E)-hexenoate 7. (C) 2002 Published by Flsevier Science Ltd.

  DOI：

  10.1016/s0957-4166(02)00180-5
• 作为产物：
  描述：

  methyl (4R,5S)-4,5-dihydroxyhex-2E-enoate 在 吡啶 、 咪唑 、 tris(dibenzylideneacetone)dipalladium(0) chloroform complex 、 sodium tetrahydroborate 、 三丁基膦 作用下， 以 1,4-二氧六环 、 水 、 N,N-二甲基甲酰胺 、 苯 为溶剂， 反应 8.0h， 生成 methyl (2E,5S)-5-{[tert-butyl(dimethyl)silyl]oxy}-2-hexenoate
  参考文献：
  名称：

  New total syntheses of (+)-macrosphelides C, F and G

  摘要：

  The total synthesis of (+)-macrosphelide C 1 (25% overall yield in nine steps), (+)-macrosphelide F 2 (20% overall yield in nine steps) and (+)-macrosphelide G 3 (22% overall yield in nine steps) has been achieved from the chemoenzymatic reaction product (4R,5S)-4-benyloxy-5-hydroxy-(2E)-hexenoate 7. (C) 2002 Published by Flsevier Science Ltd.

  DOI：

  10.1016/s0957-4166(02)00180-5

文献信息

• Synthesis of the Oviposition-Deterring Pheromone (ODP) inRhagoletis cerasi L. Preliminary communication
  作者：Beat Ernst、Beatrice Wagner

  DOI：10.1002/hlca.19890720122

  日期：1989.2.1

  For the assignment of the configuration at C(8) and C(15) of the natural oviposition-deterring pheromone 1 in Rhagoletis cerasi L., the four possible stereoisomers of 1 are synthesized. By condensing the C6 building blocks (5R)-4 and (5S)-4 with the boron enolates of the C10 building blocks (4S)-13 and (4R)-13, followed by decarboxylative dehydration, all stereoisomers of 16 are available (Scheme 5)

  为了赋予Rhogoletis cerasi L.中的天然产卵信息素1在C（8）和C（15）的构型，合成了四种可能的立体异构体1。通过将C 6结构单元（5 R）-4和（5 S）-4与C 10结构单元（4 S）-13和（4 R）-13的硼烯醇缩合，然后进行脱羧脱水，有16种立体异构体可供选择（方案5）。脱保护后，16的糖基化，随后形成牛磺酸酰胺，得到四个立体异构体（8 R，15 S）-1，（8 R，15 R）-1，（8 R，15 S）-1和（ 8 S，15 S）-1（方案6）。
• Synthesis of the 8-Hydroxy Acid of Jasplakinolide
  作者：Saengchai Wattanasereekul、Martin E. Maier

  DOI：10.1002/adsc.200404004

  日期：2004.6

  depsipeptide jasplakinolide (1) was prepared in a sequence of 13 steps from the silylated 3-hydroxy ester 6. By chain extension 6 was converted to the allyl alcohol 10. A subsequent asymmetric cyclopropanation of the allylic alcohol 10 using the Charette method provided the hydroxymethylcyclopropane 12 with excellent diastereoselectivity. This cyclopropanation was used to establish the methyl-bearing

  从甲硅烷基化的3-羟基酯6按13个步骤的顺序，制备了二十肽萘普普利特（1）中所含的受保护的ω-羟基酸4b。通过扩链6将其转化为烯丙醇10。随后使用Charette方法进行的烯丙基醇10的不对称环丙烷化为羟甲基环丙烷12提供了优异的非对映选择性。该环丙烷化用于通过（碘甲基）环丙烷14的还原环裂解在羟基酸4的C-6处建立含甲基的立体中心。烯烃15将其用于与2-甲基丙烯酸酯20的交叉烯烃复分解反应，提供烯酸酯19。所得的烯丙基碘化物24在最终的Evans烷基化步骤中用作亲电子试剂，得到ω-羟基酸衍生物26。
• Total Synthesis of Grahamimycin A₁
  作者：Kazuo Ohta、Osamu Miyagawa、Hironori Tsutsui、Oyo Mitsunobu

  DOI：10.1246/bcsj.66.523

  日期：1993.2

  grahamimycin A1 (1). The O-7–C-14 fragment [(4S,5S,7R)- or (4R,5R,7R)-7-hydroxy-4,5-isopropylidenedioxyoctanoate] was synthesized from 4,6-dideoxy-α-D-xylo -hexopyranoside. Condensation of the both fragments, followed by deprotection at the terminal hydroxyl- and carboxyl-functions afforded the seco acids of the precursors of 1. While the reaction of the seco acids having 13S-configuration with diethyl azodicarboxylate

  (3R)- 和 (3S)-3-羟基丁酸酯分别转化为 (2E,5R)- 和 (2E,5S)-5-t-丁基二甲基甲硅烷氧基-2-己烯酸，对应于 O-1-C-6 Grahamimycin A1 (1) 的片段。O-7–C-14 片段 [(4S,5S,7R)- 或 (4R,5R,7R)-7-hydroxy-4,5-isopropylidenedioxyoctanoate] 由 4,6-dideoxy-α-D-合成木糖苷。两个片段的缩合，然后在末端羟基和羧基官能团上脱保护得到前体 1 的 seco 酸。 而具有 13S-构型的 seco 酸与偶氮二羧酸二乙酯和三苯基膦的反应在低浓度下提供相应的内酯产率，具有 13R-构型的癸二酸通过 Yamaguchi 程序的大环内酯化以 56% 的产率得到所需的内酯。
• Synthesis of 1,3-dioxin-4-ones having chiral hydroxyalkyl groups at the 6-position by means of baker's yeast reduction and their uses for epc synthesis
  作者：Jun-ichi Sakaki、Yoshiaki Sugita、Masayuki Sato、Chikara Kaneko

  DOI：10.1016/s0040-4020(01)86552-2

  日期：1991.8

  Prochiral methyl ketones connected with 6-(4-oxo-1,3-dioxinyl) group directly or through methylene chain (1-3) gave, by treatment with fermenting baker's yeast, the corresponding (S)-alcohols which served as synthons for a variety of enantiomerically pure compounds.
• Formal total synthesis of grahamimycin A1
  作者：Kazuo Ohta、Oyo Mitsunobu

  DOI：10.1016/s0040-4039(00)79484-6

  日期：1991.1

  (S)-t-Butyldimethylsiloxy-2-hexenoic acid and its (R)-isomer were prepared from (S)- and (R)-3-hydroxybutanoic acid esters, respectively. Condensation of the both isomers with 2-(ptoluenesulfonyl)ethyl (4S,5S,7R)-7-hydroxy-4,5-dimethylmethylenedioxyoctanoate, synthesized from methyl 4,6-dideoxy -alpha-D-xylo-hexopyranoside, gave the corresponding esters which were converted into precursors of seco acids of grahamimycin A1 with S or R configuration at the C-6 position (grahamimycin A1 numbering). The (6S)- and (6R)-isomers were respectively subjected to macrolactonization by the use of diethyl azodicarboxylate-triphenylphosphine system or Yamaguchi procedure to afford 11, 12-dihydroxy-grahamimycin A1 whose oxidation to grahamimycin A1 has already been reported.