(2R,3S)-3,7-dimethyl-6-octene-1,2,3-triol | 121468-45-9

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (2R,3S)-3,7-dimethyl-6-octene-1,2,3-triol
• 英文别名: (2R,3S)-3,7-dimethyloct-6-ene-1,2,3-triol
• CAS: 121468-45-9
• 化学式: C₁₀H₂₀O₃
• 分子量: 188.267
• InChiKey: AAUZPDAUBFXASQ-ZJUUUORDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  13
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  60.7
• 氢给体数：
  3
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2R,3S)-3,7-dimethyl-6-octene-1,2,3-triol 在 sodium tetrahydroborate 、 四氧化锇 、 camphor-10-sulfonic acid 、 sodium hydride 、 N-甲基吗啉氧化物 、 间氯过氧苯甲酸 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 、 丙酮 、 mineral oil 为溶剂， 反应 90.42h， 生成 (2R)-2-[(2S)-5-[(4-methoxybenzyl)oxy]-2-(oxiran-2-ylmethoxy)pentan-2-yl]oxirane
  参考文献：
  名称：

  唑烷醇的主要环氧丙烷链段的合成

  摘要：

  zoapatanol的主要氧杂环庚烷片段的人类早期妊娠的线性合成，显示子宫收缩的诱导，和子宫颈扩张和子宫出血（由浓zoapatle茶），来自墨西哥zoapatle植物的叶中分离Montanoa毛白杨，从描述已知中间涉及夏普勒斯不对称环氧化，用双-环氧化物开环反应科里 Chaykovsky试剂，闭环复分解反应，和霍纳尔沃兹沃思埃蒙斯作为关键步骤烯化反应。

  DOI：

  10.1002/hlca.201200364
• 作为产物：
  描述：

  (2R,3R)-3-methyl-3-(4-methyl-3-pentenyl)oxiranemethanol 在 高氯酸 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 生成 (2R,3S)-3,7-dimethyl-6-octene-1,2,3-triol
  参考文献：
  名称：

  Total Synthesis of Thyrsiferyl 23-Acetate, a Specific Inhibitor of Protein Phosphatase 2A and an Anti-Leukemic Inducer of Apoptosis

  摘要：

  A convergent synthetic entry to the squalenoid polyether system has been developed and applied to the biologically active marine natural products thyrsiferyl 23-acetate (la), thyrsiferol (Ib), thyrsiferyl 18-acetate (Ic), and thyrsiferyl 18,23-diacetate (Id). This involved the separate construction of two advanced intermediates representing the C1-C15 (4) and C16-C24 (5) domains, followed by their organochromium-mediated coupling, installation of the tertiary alcohol at C15, and manipulation of the C18 and C23 acetate moieties. The C1-C15 (4) intermediate containing the three tetrahydropyranyl rings (A-B-C) was derived from two preconstructed tetrahydropyran-containing units representing the functionalized A (C2-C6) and C (C10-C14) rings (6 and 7, respectively). The bromotetrahydropyranyl A ring was obtained via bromoetherification of the hydroxyalkene 16, which was synthesized from (2R,3R)-epoxy geraniol. The C ring was stereoselectively constructed by acid-catalyzed opening of the hydroxy epoxide 32, derived from D-glutamic acid. Intermediates 6 and 7 were-joined using organochromium conditions, and ketone and hydroxyl functionalities were installed at carbons:7 and 11, respectively. Closure of the B ring was accomplished stereoselectively by formation of species derived from a C7, C11 keto-alcohol and in situ reduction of a tetrahydropyranyl oxonium. The complementary tetrahydrofuran D (C19-C22) ring was obtained from a geraniol-derived tertiary hydroxy alkene (44) via a stereoselective Re(VII)-induced syn-oxidative cyclization. The side chain appended to the D ring was elaborated into trans-alkenyl iodide 5 under Takai reaction conditions. CrCl2-mediated coupling of aldehyde 4 containing the secondary bromide at C3 of the natural products, with iodide 5 bearing acetate moieties at C18 and C23, installed the C15-C16 carbon-carbon bond. The resultant C15 allylic carbinol was converted into an cr,P-saturated ketone, and the final methyl group was added stereoselectively using methylmagnesium bromide. Saponification of the C18 acetate yielded la, whereas cleavage of both C18 and C23 acetates gave the triol Ib. This modular entry into the squalenoid-polyether system may facilitate further evaluation of the antileukemic, apoptosis-inducing, protein serine/threonine phosphatase 2A inhibitory and anti-multidrug resistance activities of the thyrsiferol-derived natural products.

  DOI：

  10.1021/ja000001r

文献信息

• Molybdenum-Catalyzed Hydroxyl-Directed <i>Anti</i>-Dihydroxylation of Allylic and Homoallylic Alcohols
  作者：Pei Fan、Shixia Su、Chuan Wang

  DOI：10.1021/acscatal.8b01449

  日期：2018.8.3

  A catalytic hydroxyl-directed anti-dihydroxylation of allylic and homoallylic alcohols has been developed. This operationally simple method was successfully applied to the direct anti-monodihydroxylation of allylic alcohols containing at least one distal olefinic unit. Under the catalysis of commercially available MoO2(acac)2, an array of hydroxylated dienes were successfully converted into various

  已经开发了烯丙基和均烯丙基醇的催化羟基定向的抗二羟基化。这种操作简单的方法已成功地应用于含有至少一个远端烯烃单元的烯丙基醇的直接抗单二羟基化反应。在市售MoO 2（acac）2的催化下，使用过氧化氢作为环境良性氧化剂，在有氧条件下，特别是在完全区域选择性和氢键作用下，成功地将一系列羟基化的二烯成功转化为各种1,2,3-三醇。大多数情况下采用非对映特异性途径。
• Synthesis of the aggregation pheromone of the Colorado potato beetle from its degradation product
  作者：Weronika Wacławczyk-Biedroń、Bożena Frąckowiak-Wojtasek、Daniel Strub、Magdalena Rzechak、Hubert Wojtasek

  DOI：10.1016/j.bmcl.2015.06.083

  日期：2015.9

  Incubation of the Colorado potato beetle aggregation pheromone, (S)-1,3-dihydroxy-3,7-dimethyl-6-octen-2-one, with antennal or leg extracts from this beetle gave 6-methyl-5-hepten-2-one as the major product. This ketone was used as a substrate in a stereoselective synthesis of the pheromone. It was attached to the butanediacetal of glycolic acid with good stereoselectivity and the desired isomer was

  将科罗拉多马铃薯甲虫聚集信息素（S）-1,3-二羟基-3,7-二甲基-6-辛烯-2-酮与该甲虫的触角或腿部提取物一起孵育，得到6-甲基-5-庚烯-二合一为主要产品。该酮用作信息素的立体选择性合成中的底物。将其以良好的立体选择性连接到乙醇酸的丁二缩醛上，并通过在硅胶上纯化该反应的产物来进一步富集所需的异构体。
• A protecting group-free synthesis of the Colorado potato beetle pheromone
  作者：Zhongtao Wu、Manuel Jäger、Jeffrey Buter、Adriaan J Minnaard

  DOI：10.3762/bjoc.9.273

  日期：——

  A novel synthesis of the aggregation pheromone of the Colorado potato beetle, Leptinotarsa decemlineata, has been developed based on a Sharpless asymmetric epoxidation in combination with a chemoselective alcohol oxidation using catalytic [(neocuproine)PdOAc]₂OTf₂. Employing this approach, the pheromone was synthesized in 3 steps, 80% yield and 86% ee from geraniol.

  基于Sharpless不对称环氧化和化学选择性醇氧化的组合，利用催化[(neocuproine)PdOAc]₂OTf₂，开发了一种新的合成科罗拉多马铃薯甲虫聚集信息素的方法。采用这种方法，从香叶醇出发，经过3个步骤，得到甲虫聚集信息素，产率为80%，ee为86%。
• Catalytic asymmetric synthesis of the Colorado potato beetle pheromone and its enantiomer
  作者：Shuo-Ning Li、Ling-Lan Fang、Jiang-Chun Zhong、Jun-Jian Shen、Hao Xu、Yan-Qing Yang、Shi-Cong Hou、Qing-hua Bian

  DOI：10.1016/j.tetasy.2013.12.018

  日期：2014.4

  An efficient catalytic asymmetric synthesis of the CPB pheromone [(S)-1,3-dihydroxy-3,7-dimethy1-6-octen-2-one] and its enantiomer was accomplished with 99% ee and in gram quantities from geraniol. The key steps in this procedure involve Sharpless asymmetric epoxidation and recrystallization of the 4-bromobenzoate from the CPB pheromone to improve its enantiomeric purity. Furthermore, the absolute configuration of the CPB pheromone enantiomer was confirmed as (R) for the first time by the X-ray crystallographic structure of its benzoate. (C) 2014 Elsevier Ltd. All rights reserved.
• Diastereocontrol in the Reaction of (R)-2,2-Dimethyl-4-acyl-1,3-dioxolanes with Alkylmetals: A Facile Entry to Enantiopure Terpenetriols
  作者：Takeshi Nakai、Hisashi Mikoshiba、Koichi Mikami

  DOI：10.3987/com-00-s(i)76

  日期：——