5-甲基-己-4-烯-2-醇 | 3695-33-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 5-甲基-己-4-烯-2-醇
• 英文名称: 5-methylhex-4-en-2-ol
• 英文别名: 2-Methyl-hexen-(2)-ol-(5)
• CAS: 3695-33-8
• 化学式: C₇H₁₄O
• 分子量: 114.188
• InChiKey: LVKFVRBJGDAPIH-UHFFFAOYSA-N

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

上下游信息

• 下游产品

  中文名称	英文名称	CAS号	化学式	分子量
  ——	(R)-5-methyl-4-hexene-2-ol	157225-71-3	C7H14O	114.188

反应信息

• 作为反应物：
  描述：

  5-甲基-己-4-烯-2-醇 在 铂 氢气 作用下， 以 甲醇 为溶剂， 生成 5-甲基-2-己醇
  参考文献：
  名称：

  Julia,M. et al., Bulletin de la Societe Chimique de France, 1960, p. 1735 - 1739

  摘要：

  DOI：
• 作为产物：
  描述：

  5-甲基-3,4-己二烯-2-醇 反应 132.0h， 以50%的产率得到5-甲基-己-4-烯-2-醇
  参考文献：
  名称：

  减少烯丙醇

  摘要：

  α-烯丙醇被还原成相应的β-烯醇，而β-烯丙醇经历异构化而导致它们的γ-炔属对应物。

  DOI：

  10.1016/s0040-4039(00)82117-6

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。
• Interactive design and synthesis of a novel antibacterial agent
  作者：Saul Wolfe、Haolun Jin、Kiyull Yang、Chan-Kyung Kim、Ernest McEachern

  DOI：10.1139/v94-133

  日期：1994.4.1

  β-Lactam compounds act on penicillin-recognizing enzymes via acylation of the hydroxyl group of an active site serine. When the resulting acyl enzyme is kinetically stable, as in the case of a penicillin-binding protein (PBP), the biosynthesis of a bacterial cell wall is inhibited, and death of the organism results. The de novo design of an antibacterial agent targeted to a PBP might be possible if the three-dimensional structural requirements of the equilibrium (i.e, fit) and catalytic (i.e. reactivity) steps of the aforementioned enzymatic process could be determined. For a model of the active site of a PBP from Streptomyces R61, the use of molecular mechanics calculations to treat "fit," and ab initio molecular orbital calculations to treat "reactivity," leads to the idea that the carboxyl group (G₁) and the amide N-H (G₂) of the antibiotic are hydrogen bonded to a lysine amino group and a valine carbonyl group in the enzyme–substrate complex. These two hydrogen bonds place the serine hydroxyl group on the convex face of the antibiotic, in position for attack on the β-lactam ring by a neutral reaction, catalyzed by water, that involves a direct proton transfer to the β-lactam nitrogen. Molecular orbital calculations of structure–reactivity relations associated with this mechanism suggest that C=N is bioisosteric to the β-lactam N-C(=O), comparable to a β-lactam in its reactivity with an alcohol, and that the product RO(C-N)H is formed essentially irreversibly (−ΔE > 10 kcal/mol). Accordingly, structures containing a G₁ and a G₂ separated by a C=N, and positioned in different ways with respect to this functional group, have been synthesized computationally and examined for their ability to fit to the PBP model. This strategy identified a 2H-5,6-dihydro-1,4-thiazine substituted by hydroxyl and carboxyl groups as a target for chemical synthesis. However, exploratory experiments suggested that the C=N of this compound equilibrates with endocyclic and exocyclic enamine tautomers. This required that the C2 position be substituted, and that the hydroxyl group not be attached to the carbon atom adjacent to the C=N. These conditions are met in a 2,2-dimethyl-3-(2-hydroxypropyl)-1,4-thiazine, which also exhibits the necessary fit to the PBP model. Two epimers of this compound have been synthesized, from D- and L-serine. The compound derived from L-serine is not active. The compound derived from D-serine exhibits antibacterial activity, but is unstable, and binding studies with PBP's have not been performed. It is hoped that these studies can be carried out if modification of the lead structure leads to compounds with improved chemical stability.

  β-内酰胺化合物通过酰化活性位点丝氨酸的羟基作用于青霉素识别酶。当产生的酰酶在动力学上是稳定的，如青霉素结合蛋白（PBP）的情况下，细菌细胞壁的生物合成被抑制，导致生物体的死亡。如果能确定青霉素结合蛋白的三维结构要求（即平衡的适合性）和催化（即反应性）步骤的需求，可能会实现针对PBP的抗菌剂的全新设计。对来自链霉菌R61的PBP的活性位点模型，使用分子力学计算处理“适合性”，并使用从头算分子轨道计算处理“反应性”，得出一个想法，即抗生素的羧基（G1）和酰胺N-H（G2）与酶-底物复合物中的赖氨酸氨基团和缬氨酸羰基团形成氢键。这两个氢键将丝氨酸羟基置于抗生素的凸面上，处于通过中性反应由水催化的直接质子转移至β-内酰胺氮原子的位置。与这种机制相关的结构-反应关系的分子轨道计算表明，C=N与β-内酰胺N-C(=O)是生物等同物，与醇类反应时与β-内酰胺相当，产物RO(C-N)H基本上是不可逆的（−ΔE > 10 kcal/mol）。因此，含有由C=N分隔的G1和G2的结构，并以不同方式相对于这个功能团定位的结构已经通过计算合成并检验其适合于PBP模型的能力。这种策略确定了一个被羟基和羧基取代的2H-5,6-二氢-1,4-噻嗪作为化学合成的目标。然而，探索性实验表明，该化合物的C=N与内环和外环烯胺互变异构体平衡。这要求对C2位置进行取代，并且羟基不能连接到邻近C=N的碳原子。这些条件在2,2-二甲基-3-(2-羟基丙基)-1,4-噻嗪中得到满足，该化合物还展现出与PBP模型的必要适合性。这种化合物的两个对映体已经从D-丝氨酸和L-丝氨酸合成。从L-丝氨酸衍生的化合物不活跃。从D-丝氨酸衍生的化合物表现出抗菌活性，但不稳定，并且尚未进行与PBP的结合研究。希望如果引物结构的修改导致具有改善化学稳定性的化合物，这些研究可以进行。
• Deacylative transformations of ketones via aromatization-promoted C–C bond activation
  作者：Yan Xu、Xiaotian Qi、Pengfei Zheng、Carlo C. Berti、Peng Liu、Guangbin Dong

  DOI：10.1038/s41586-019-0926-8

  日期：2019.3

  3-dienes. Specifically, the acyl group is removed from the ketone and transformed to a pyrazole, and the resulting alkyl fragment undergoes various transformations. These include the deacetylation of methyl ketones, carbenoid-free formal homologation of aliphatic linear ketones and deconstructive pyrazole synthesis from cyclic ketones. Given that ketones are prevalent in feedstock chemicals, natural products

  碳-氢（C-H）键和碳-碳（C-C）键是有机物的主要成分。C-H 功能化技术的最新进展极大地扩展了我们的有机合成工具箱。相比之下，能够编辑分子骨架的 C-C 激活方法仍然有限2-7。已经提出了几种催化 C-C 活化的方法，特别是使用酮底物，通常通过使用环应变释放作为热力学驱动力 4,6 或引导基团 5,7 来控制反应结果来促进这些方法。虽然有效，但这些策略需要包含高度应变的酮或预安装的导向基团的底物，或者仅限于更专业的底物类别 5。在这里，我们报告了由原位形成的前芳香族中间体的芳构化驱动的一般 C-C 活化模式。该反应适用于各种酮底物，由铱/膦组合催化，并由肼试剂和 1,3-二烯促进。具体而言，将酰基从酮中除去并转化为吡唑，并且所得烷基片段经历各种转化。这些包括甲基酮的脱乙酰化、脂肪族线性酮的无类卡宾正式同系化和从环酮中解构吡唑合成。鉴于酮在原料化学品、天然产品和药物中很普遍，这些转化可以
• COOLING SENSATION AGENT COMPOSITION, SENSORY STIMULATION AGENT COMPOSITION AND USE OF THE SAME
  申请人：Komatsuki Yasuhiro

  公开号：US20110081393A1

  公开（公告）日：2011-04-07

  Disclosed is a cooling sensation agent composition or sensory stimulation agent composition which contains at least one of diester compounds of dicarboxylic acid represented by the formula (1) wherein A represents CH 2 or CH═CH, n represents an integer of 0 to 4 when A is CH 2 , or 1 when A is CH═CH, B is an alcohol residue having 10 to 18 carbon atoms and containing a para-menthane skeleton, which may have a substituent, and C is an alcohol residue having 6 to 18 carbon atoms, which may have a substituent as well as a flavor or fragrance composition, a beverage, a food product, a perfume or cosmetic product, a toiletry product, daily utensil products or groceries, a fiber, a fiber product, clothes, clothing or a medicine, wherein the cooling sensation agent composition or the sensory stimulation agent composition is compounded.

  本文披露了一种包含以下化学式（1）所代表的二羧酸双酯化合物之一的冷却感剂组合物或感官刺激剂组合物，其中A代表CH2或CH═CH，n代表整数0至4（当A为CH2时）或1（当A为CH═CH时），B是含有10至18个碳原子并含有对蒎烷骨架的醇残基，可能有取代基，C是含有6至18个碳原子的醇残基，可能也有取代基，以及香料或香精组合物、饮料、食品产品、香水或化妆品产品、洗涤用品、日用品或杂货、纤维、纤维制品、衣服、服装或药品，其中复合了冷却感剂组合物或感官刺激剂组合物。
• Reduction d'alcools alleniques par l'hydrure et le methoxy hydrure de lithium et d'aluminium
  作者：R. Baudouy、J. Gore

  DOI：10.1016/0040-4020(75)80049-4

  日期：1975.1