(R/S)-3-methyl-5-hexene-1,3-diol | 114580-75-5

• 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: (R/S)-3-methyl-5-hexene-1,3-diol
• 英文别名: 3-methyl-5-hexene-1,3-diol；3-methylhex-5-ene-1,3-diol；3-methyl-5-hexen-1,3-diol；3-methyl-hex-5-ene-1,3-diol；3-Methyl-hex-5-en-1,3-diol；1.3-Dihydroxy-3-methyl-hexen-(5)
• CAS: 114580-75-5
• 化学式: C₇H₁₄O₂
• 分子量: 130.187
• InChiKey: XRBODZLBHMHWOK-UHFFFAOYSA-N

物化性质

• 沸点：
  102-104 °C(Press: 5 Torr)
• 密度：
  0.969±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  9
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (R/S)-3-methyl-5-hexene-1,3-diol 在 lead(IV) acetate 、 4-二甲氨基吡啶 、 sodium hydroxide 、 potassium permanganate 、 四氧化锇 、 N-甲基吗啉氧化物 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 、 phosphate buffer 、 乙醚 、 二氯甲烷 、 水 、 甲苯 、 叔丁醇 为溶剂， 反应 91.0h， 生成 甲瓦龙酸内酯
  参考文献：
  名称：

  羟基取代季碳中心的催化对映选择性途径：用催化抗体解析叔醇

  摘要：

  研究了醛缩酶抗体 38C2 催化的三级醛缩分解。三级羟醛被证明是用于抗体催化的逆羟醛反应的非常好的底物。抗体对这些反应的催化效率 (kcat/KM)/kuncat 约为 1010 M-1。荧光叔醛醇允许对映体过量作为反应转化的函数进行定量研究，揭示了约的 E 值。在这种情况下为 160。对各种底物的研究表明，抗体催化的逆醛醇化可快速进入高度对映异构体富集的叔醛醇，通常>95% ee，含有结构不同的杂原子取代的季碳中心。这种方法对天然产物合成的效用已通过 (+)-frontalin 的合成得到证明，

  DOI：

  10.1021/ja991507g
• 作为产物：
  描述：

  3-methyl-1-(tetrahydro-2-pyranyloxy)-5-hexen-3-ol 在 盐酸 作用下， 生成 (R/S)-3-methyl-5-hexene-1,3-diol
  参考文献：
  名称：

  Tamura; Takai, Journal of the Agricultural Chemical Society of Japan, 1957, vol. 21, p. 260

  摘要：

  DOI：

文献信息

• Facile Preparation of Allylzinc Species from Allyl Bromides and Unactivated Zinc Induced by a Catalytic Amount of Aluminum Chloride and Their Reactions with Carbonyl Compounds and Acetals.
  作者：Hatsuo MAEDA、Kazushige SHONO、Hidenobu OHMORI

  DOI：10.1248/cpb.42.1808

  日期：——

  The effects of Lewis acids (ZnCl2, AlCl3, BF3, and TiCl4) on the generation of allylzinc species from allyl bromide and unactivated zinc powder in dry tetrahydrofuran (THF) were examined by trapping the organozinc compound with benzaldehyde, that is, Grignard-type allylation of the aldehyde. Among the Lewis acids employed, AlCl3, was found to be the promoter of choice. The allylzinc species preformed in the presence of a catalytic amount of AlCl3 effectively allylated carbonyl compounds. Various aromatic and aliphatic aldehydes as well as ketones were converted into homoallylic alcohols in good to excellent yields. Under the reaction conditions employed, ester, hydroxy, acetal, and aromatic nitro and halide groups were tolerated. In the case of α, β-unsaturated carbonyl compounds, selective 1, 2-addition was observed. Substituted allyl bromides such as prenyl, crotyl, cinnamyl, and 2-cyclohexenyl bromides were smoothly converted to the corresponding allylzinc compounds, which reacted with carbonyl compounds to give substituted homoallylic alcohols in excellent yields. The diastereoselectivity in crotylation, cinnamylation, and 2-cyclohexenylation depended upon the structures of both the organic metals and the electrophiles. The origin of the observed selectivity is discussed. The allylation of dimethyl and cyclic acetals accompanied with carbon-oxygen bond cleavege also proceeded in excellent yields provided that two equivalents of AlCl3 was present.

  在干燥的四氢呋喃（THF）中，研究了路易斯酸（ZnCl2、AlCl3、BF3和TiCl4）对烯丙基溴和未活化的锌粉生成烯丙基锌物种的影响，并通过苯甲醛捕获有机锌化合物，即醛的格氏型烯丙基化反应。在所用的路易斯酸中， 被发现是最优的促进剂。在催化量的 存在下预形成的烯丙基锌物种能有效地烯丙基化羰基化合物。各种芳香族和脂肪族醛以及酮被转化为同烯丙基醇，产率良好至优秀。在所采用的反应条件下，酯、羟基、缩醛以及芳香族硝基和卤素基团均被容忍。对于α,β-不饱和羰基化合物，观察到了选择性的1,2-加成。取代的烯丙基溴如香叶基、巴豆基、肉桂基和2-环己烯基溴均能顺利转化为相应的烯丙基锌化合物，这些化合物与羰基化合物反应生成取代的同烯丙基醇，产率极佳。在巴豆基化、肉桂基化和2-环己烯基化中的立体选择性取决于有机金属和亲电试剂的结构。讨论了观察到的选择性的起源。在 的两当量存在下，伴随着碳-氧键断裂的二甲基和环状缩醛的烯丙基化也以极佳的产率进行。
• Partial Synthesis of 3?-Hydroxy-2?-deoxy-2?,3?,4?,5?-tetrahydroverrucarin A. Verrucarins and roridins, 38th Communication [1]
  作者：Eric-Andr�a Notegen、Motoo Tori、Christoph Tamm

  DOI：10.1002/hlca.19810640132

  日期：1981.2.4

  The macrocyclic trichothecene triester 3′-hydroxy-2′-deoxy-2",3",4",5"-tetrahydroverrucarin A (37), has been synthesized starting from the sesquiterpene alcohol verrucarol (3), adipic acid and a derivative of mevalonic acid (14). The latter has been prepared from 4-(tetrahydro-2-pyranyloxy)-2-butanone (9).

  从倍半萜烯醇香豆酚（3），己二酸和其衍生物开始合成了大环三茂萜三酯3'-羟基-2'-脱氧-2“，3”，4“，5”-四氢过钌carin A（37）。甲羟戊酸（14）。后者由4-（四氢-2-吡喃氧基）-2-丁酮（9）制备。
• Machleidt,H. et al., Justus Liebigs Annalen der Chemie, 1962, vol. 655, p. 70 - 80
  作者：Machleidt,H. et al.

  DOI：——

  日期：——
• Ferraboschi, Patrizia; Canevotti, Renato; Grisenti, Paride, Journal of the Chemical Society. Perkin transactions I, 1987, p. 2301 - 2304
  作者：Ferraboschi, Patrizia、Canevotti, Renato、Grisenti, Paride、Santaniello, Enzo

  DOI：——

  日期：——
• Synthesis of (S)-(+)-mevalonolactone and mevalonate analogs
  作者：Veronique Bolitt、Charles Mioskowski、R. K. Bhatt、J. R. Falck

  DOI：10.1021/jo00013a030

  日期：1991.6

  Tetrahydropyran (R/S)-1, a vinylidene analogue of mevalonolactone, was prepared by addition of excess allyl Grignard to 4-acetoxy-2-butanone, iodoetherification of the resultant diol 5, and DBN-mediated dehydrohalogenation. Sharpless asymmetric epoxidation of 3-methylhexa-2,5-dien-1-ol (9) gave epoxide 10 that was reduced to diol 11 (> 95% ee) by LiA1H4. Annulation and elimination of HI as described for 5 furnished (S)-1. Ozonolysis of (S)-1 yielded (S)-mevalonolactone (2), whereas bromomethoxylation and controlled hydrolysis led to 3, a reactive analogue of (S)-mevalonic acid. Analogue 4, a nonionizable lipophilic version of (S)-mevalonic acid, was generated upon exposure of (S)-1 or 2 to excess Tebbe-Grubbs reagent.