(S)-5-methyl-4-hexene-2-ol | 157225-72-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (S)-5-methyl-4-hexene-2-ol
• 英文别名: (S)-5-Methyl-4-hexen-2-ol；5-methyl-hex-4-en-2-ol；(2S)-5-methylhex-4-en-2-ol
• CAS: 157225-72-4
• 化学式: C₇H₁₄O
• 分子量: 114.188
• InChiKey: LVKFVRBJGDAPIH-ZETCQYMHSA-N

物化性质

• 沸点：
  158.7±9.0 °C(Predicted)
• 密度：
  0.843±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  8
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (S)-5-methyl-4-hexene-2-ol 在 叔丁基过氧化氢 、 六甲基磷酰三胺 、 sodium tetrahydroborate 、 Grubbs catalyst first generation 、 N-甲基吲哚酮 、 cerium(III) chloride 、 四丙基高钌酸铵 、 bis(acetylacetonate)oxovanadium 、 三乙胺 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲醇 、 癸烷 、 二氯甲烷 为溶剂， 反应 105.0h， 生成 3-ethyl-6-[2-(4-methoxy-benzyloxy)-propyl]-5-methyl-3,6-dihydro-pyran-2-one
  参考文献：
  名称：

  Synthesis of the C12−C19 Fragment of (+)-Peloruside A through a Diastereomer-Discriminating RCM Reaction

  摘要：

  A short and efficient asymmetric synthesis of the C12-C19 fragment of the cytotoxic macrolide (+)-peloruside A has been achieved via a highly diastereomer-discriminating RCM of alpha-branched but-3-enoate ester of a methallylic alcohol derived from hydrolytically resolved (S)-(-)-propylene oxide.

  DOI：

  10.1021/ol050588k
• 作为产物：
  描述：

  2-Methyl-1-Propenylmagnesium Bromide 、 S-环氧丙烷 在 copper(l) iodide 作用下， 以 四氢呋喃 为溶剂， 反应 0.25h， 以87%的产率得到(S)-5-methyl-4-hexene-2-ol
  参考文献：
  名称：

  Synthesis of the C12−C19 Fragment of (+)-Peloruside A through a Diastereomer-Discriminating RCM Reaction

  摘要：

  A short and efficient asymmetric synthesis of the C12-C19 fragment of the cytotoxic macrolide (+)-peloruside A has been achieved via a highly diastereomer-discriminating RCM of alpha-branched but-3-enoate ester of a methallylic alcohol derived from hydrolytically resolved (S)-(-)-propylene oxide.

  DOI：

  10.1021/ol050588k

文献信息

• Synthesis of the stereoisomers of a novel antibacterial agent and interpretation of their relative activities in terms of a theoretical model of the penicillin receptor
  作者：Saul Wolfe、Caijun Zhang、Blair D. Johnston、Chan-Kyung Kim

  DOI：10.1139/v94-134

  日期：1994.4.1

  2,2-Dimethyl-3-(2′-hydroxypropyl)-5-carboxy-Δ³ -1,4-thiazine (1) is a designed antibacterial agent. Based on an analysis of how penicillin complexes to and reacts with a model of a penicillin-binding protein, 1 contains a functional group (C=N) that can react with a serine hydroxyl group of the receptor according to the putative reaction Enz-OH + C = N → Enz-O-C-NH. Compound 1 also contains additional substituents that are designed to position the O-H and C=N groups relative to one another in the enzyme–substrate complex in a geometry that attempts to reproduce the optimum geometry of approach of two such reactants. A most important assumption is that this optimum geometry can be computed ab initio. In a first preparation of 1, (±)-5-methyl-4-hexene-2-ol (2) was converted to the lithium salt of (±)-2-mercapto-2-methyl-5-tert-butyldimethylsiloxy-3- hexanone (7), which was condensed with the N-tert-butoxycarbonyl-D- and L-serine-β-lactones (3). The synthesis was completed by deprotection with formic acid and cyclization in water. The R and S enantiomers of 2 have now been obtained, and the absolute configuration of the alcohol established, by reaction of the R- and S-propylene oxides with an organometallic reagent prepared from β,β-dimethylvinyl bromide. The R alcohol has also been secured by lipase-catalyzed transesterification with trifluoroethyl butyrate, and chemical hydrolysis of the trifluoroethyl ester. The R and S enantiomers of 2 were converted to the R and S enantiomers of 7, and these were condensed with the R and S enantiomers of 3 to yield each of the stereoisomers of the chemically unstable 1 in ca. 95% optically pure form. Antibacterial activity resides in the 5S,8R and 5S,8S isomers. These findings are shown to be consistent with the theoretical model. It is hoped that the stability of the lead structure 1 can be improved, to allow binding experiments with penicillin recognizing enzymes to proceed.

  2,2-二甲基-3-(2'-羟丙基)-5-羧基-Δ³-1,4-噻嗪（1）是一种设计的抗菌剂。根据对青霉素与青霉素结合蛋白模型的复合物如何反应的分析，1含有一个功能基团（C=N），可以根据假定的反应Enz-OH + C = N → Enz-O-C-NH与受体的丝氨酸羟基反应。化合物1还包含额外的取代基，旨在将O-H和C=N基团相对于酶-底物复合物中的位置设计成一种几何构型，试图重现两种反应物的最佳接近几何构型。一个最重要的假设是这种最佳几何构型可以从头计算。在对1的第一次制备中，（±）-5-甲基-4-己烯-2-醇（2）被转化为（±）-2-巯基-2-甲基-5-叔丁基二甲基硅氧基-3-己酮（7）的锂盐，然后与N-叔丁氧羰基-D-和L-丝氨酸-β-内酯（3）缩合。合成完成后，用甲酸去保护，然后在水中环化。2的R和S对映体现已被获得，并通过R-和S-丙烯氧化物与由β，β-二甲基乙烯基溴制备的有机金属试剂反应，确定了醇的绝对构型。R醇也通过脂肪酶催化的三氟乙基丁酸酯转酯化和三氟乙基酯的化学水解获得。2的R和S对映体转化为7的R和S对映体，然后与3的R和S对映体缩合，以在约95%光学纯度形式中产生化学不稳定的1的各立体异构体。抗菌活性存在于5S,8R和5S,8S异构体中。这些发现与理论模型一致。希望可以改进引物结构1的稳定性，以便进行与识别青霉素的酶的结合实验。
• Synthesis of the C12−C19 Fragment of (+)-Peloruside A through a Diastereomer-Discriminating RCM Reaction
  作者：Emmanuel Roulland、Mikhail S. Ermolenko

  DOI：10.1021/ol050588k

  日期：2005.5.1

  A short and efficient asymmetric synthesis of the C12-C19 fragment of the cytotoxic macrolide (+)-peloruside A has been achieved via a highly diastereomer-discriminating RCM of alpha-branched but-3-enoate ester of a methallylic alcohol derived from hydrolytically resolved (S)-(-)-propylene oxide.