(5R)-6-benzyloxy-5-methyl-4-hydroxyhex-1-ene | 89046-67-3

• 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: (5R)-6-benzyloxy-5-methyl-4-hydroxyhex-1-ene
• 英文别名: (2R)-2-methyl-1-phenylmethoxyhex-5-en-3-ol
• CAS: 89046-67-3；91796-47-3；91796-48-4；91798-02-6；91798-03-7；94233-73-5；94233-74-6；106357-32-8
• 化学式: C₁₄H₂₀O₂
• 分子量: 220.312
• InChiKey: YKXXUQVVHYEXKT-PUODRLBUSA-N

物化性质

• 沸点：
  339.4±30.0 °C(Predicted)
• 密度：
  0.996±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  16
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (5R)-6-benzyloxy-5-methyl-4-hydroxyhex-1-ene 在 palladium on activated charcoal 咪唑 、 sodium tetrahydroborate 、 samarium diiodide 、 四丁基氟化铵 、 氢气 、 戴斯-马丁氧化剂 、 臭氧 、 N,N-二异丙基乙胺 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 四氢呋喃 、 二氯甲烷 、 乙酸乙酯 、 N,N-二甲基甲酰胺 、 苯 为溶剂， 反应 48.0h， 生成 [(3S,4R,5R)-5-hydroxy-4,6-dimethyl-1-(2-trimethylsilylethoxymethoxy)hept-6-en-3-yl] benzoate
  参考文献：
  名称：

  Synthetic studies toward ansatrienines: application of the Evans–Tishchenko reaction to chiral enones

  摘要：

  Practical syntheses of the C9-C14 sterotriade 5 and the C1-C8 polyene unit 6 in ansatrienine A (mycotriene) (la), and other ansamycin antibiotics is described. A key step for controlling the configuration of the stereogenic center at C13 involves the stereoselective reduction of enone 10 using the Evans-Tishchenko reaction. (C) 1999 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(99)00069-5
• 作为产物：
  描述：

  methyl (2R)-3-(benzyloxy)-2-methylpropanoate 在 四氯化钛 、 二异丁基氢化铝 作用下， 以 二氯甲烷 为溶剂， 反应 1.5h， 生成 (5R)-6-benzyloxy-5-methyl-4-hydroxyhex-1-ene
  参考文献：
  名称：

  Synthetic studies toward ansatrienines: application of the Evans–Tishchenko reaction to chiral enones

  摘要：

  Practical syntheses of the C9-C14 sterotriade 5 and the C1-C8 polyene unit 6 in ansatrienine A (mycotriene) (la), and other ansamycin antibiotics is described. A key step for controlling the configuration of the stereogenic center at C13 involves the stereoselective reduction of enone 10 using the Evans-Tishchenko reaction. (C) 1999 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(99)00069-5

文献信息

• Total Synthesis of Rhizoxin D, a Potent Antimitotic Agent from the Fungus <i>Rhizopus chinensi</i>s
  作者：James D. White、Paul R. Blakemore、Neal J. Green、E. Bryan Hauser、Mark A. Holoboski、Linda E. Keown、Christine S. Nylund Kolz、Barton W. Phillips

  DOI：10.1021/jo020537q

  日期：2002.11.1

  configuration at C5 of 2 through a stereoselective addition of the radical derived from dehalogenation of 21 at the beta carbon of the (Z)-alpha,beta-unsaturated ester. Aldehyde 29 was obtained from phenylthioacetal 24 and condensed with phosphorane 30, representing subunit B, in a Wittig reaction that gave the (E,E)-dienoate 31. This ester was converted to aldehyde 33 in preparation for coupling with

  根霉菌素D（2）由分别代表C3-C9，C10-C13，C14-C19和C20-C27的四个亚基A，B，C和D合成。亚基A是通过碘代乙缩醛21的环化制备的，该碘代乙缩醛21通过在（Z）-α，β-不饱和酯的β碳上立体选择性地添加衍生自21的脱卤基团而将C5的构型设定为2。乙醛29从苯硫缩醛24中获得，并在代表Wittig的Wittig反应中与代表亚基B的磷烷30缩合。该酯被转化为醛33，以准备与亚基C偶联。由炔丙醇经六步获得甲基酮形式的甲基酮55。33的醇醛缩醛反应与用（+）-DIPCl制备的55的烯醇缩醛反应，得到具有（13S）-构型的期望的β-羟基酮56，与（13R）-非对映异构体的比率为17-20：1。还原成抗二醇57并作为TIPS醚58进行选择性保护后，将C15羟基酯化得到膦酸酯59。衍生自δ-内酯60的醛62的分子内Wadsworth-Emmons反应提供了大内酯63，该大内酯63在
• Synthetic Studies on a Marine Natural Product, Palmerolide A: Synthesis of C1-C9 and C15-C21 Fragments
  作者：Krishna Kaliappan、Parthasarathy Gowrisankar

  DOI：10.1055/s-2007-982539

  日期：2007.6

  An efficient cross metathesis and Pd-catalyzed allylic rearrangement have been successfully used to construct the northern hemisphere of a cytotoxic marine natural product, palmerolide A.

  有效的交叉复分解和 Pd 催化的烯丙基重排已成功用于构建具有细胞毒性的海洋天然产物 Palmerolide A 的北半球。
• Synthetic studies toward rapamycin: a solution to a problem in chirality merger through use of the Ireland reaction
  作者：Matthew J. Fisher、Cheryl D. Myers、Jesus Joglar、Shu Hui Chen、Samuel J. Danishefsky

  DOI：10.1021/jo00020a026

  日期：1991.9

  A program directed toward a total synthesis of rapamycin is described. This paper reports the synthesis of enoate 36, a fragment that would correspond to carbons 28-49 of rapamycin. The two building blocks required to reach 36 were allylic alcohol 5 and acid 6. The former was obtained in a straightforward way from D-(+)-glucose. The route passed through a 5,6-methylene derivative (see structure 12) that underwent Ferrier transformation to the hydroxycyclohexanone derivative 13. The acid 6 was built from aldehyde 15. An addition reaction of allyltrimethylsilane to 15 and a subsequent addition of crotylboronate 18 to aldehyde 17 were the key steps in the chain extension leading to the acid. The central issue of the synthesis was the merging of two chiral sectors (see A and B) to produce an ensemble in which the achiral spacer element consists of a single methylene carbon, C39. This problem was solved by establishing an ester bond between 5 and 6. The strategic C40-C39 carbon-carbon bond was generated by application of the Ireland ester enolate rearrangement. The extraneous carboxyl group (see structure 28) was removed by photolysis of the N-hydroxyphthalimide ester (see transformation 30 --> 31).
• Synthetic studies toward ansatrienines: application of the Evans–Tishchenko reaction to chiral enones
  作者：Kai-Uwe Schöning、R.K Hayashi、Douglas R Powell、Andreas Kirschning

  DOI：10.1016/s0957-4166(99)00069-5

  日期：1999.3

  Practical syntheses of the C9-C14 sterotriade 5 and the C1-C8 polyene unit 6 in ansatrienine A (mycotriene) (la), and other ansamycin antibiotics is described. A key step for controlling the configuration of the stereogenic center at C13 involves the stereoselective reduction of enone 10 using the Evans-Tishchenko reaction. (C) 1999 Elsevier Science Ltd. All rights reserved.