Acetic acid (R)-2-hydroxy-2-[(2S,5R)-5-(1-hydroxy-1-methyl-ethyl)-2-methyl-tetrahydro-furan-2-yl]-ethyl ester | 78654-54-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧烷类
• 英文名称: Acetic acid (R)-2-hydroxy-2-[(2S,5R)-5-(1-hydroxy-1-methyl-ethyl)-2-methyl-tetrahydro-furan-2-yl]-ethyl ester
• 英文别名: [(2R)-2-hydroxy-2-[(2S,5R)-5-(2-hydroxypropan-2-yl)-2-methyloxolan-2-yl]ethyl] acetate
• CAS: 78654-54-3
• 化学式: C₁₂H₂₂O₅
• 分子量: 246.304
• InChiKey: SNDPUZWEPSBDDL-FOGDFJRCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  17
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  76
• 氢给体数：
  2
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  顺-3,7-二甲基-2,6-辛二烯-1-醇乙酸酯 在 sodium periodate 、 四氧化锇 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 16.0h， 以53%的产率得到Acetic acid (R)-2-hydroxy-2-[(2S,5R)-5-(1-hydroxy-1-methyl-ethyl)-2-methyl-tetrahydro-furan-2-yl]-ethyl ester
  参考文献：
  名称：

  OsO 4-乙酸香叶酯和乙酸甘油酯催化氧化成顺式-2,5-双（羟甲基）四氢呋喃

  摘要：

  的OsO 4催化1,5-二烯乙酸香叶酯（的氧化环化1）和乙酸橙花酯（2）与顺式-2,5-双（羟甲基）四氢呋喃3和4分别在的NaIO的存在4作为共氧化剂在DMF中。该反应是立体特异性的，并且在原料的两个双键上依次顺式加成。观察到的立体选择性可以通过调用已被分离和表征的基于正方形的金字塔形（（VI）二酯（5）的中间体来解释。有证据表明，该物质确实是转化过程中的一种中间产物。1到3。

  DOI：

  10.1016/s0040-4039(98)02172-8

文献信息

• Reactions of 1,5-Dienes with Ruthenium Tetraoxide: Stereoselective Synthesis of Tetrahydrofurandiols
  作者：Laura Albarella、Domenica Musumeci、Donato Sica

  DOI：10.1002/1099-0690(200103)2001:5<997::aid-ejoc997>3.0.co;2-7

  日期：2001.3

  stereoselectively by syn oxygen addition to both double bonds. The formation of tetrahydrofuran derivatives is presumed to involve initial addition of RuO4 to one double bond of the 1,5-diene to give a ruthenium(VI) diester, which subsequently undergoes conversion into the cyclic ether with participation of the second double bond.

  使用0.05当量的四氧化钌催化氧化1,5-二烯的改进方法。催化剂RuO 2 ·2H 2 O的当量，2.5当量。介绍了作为化学计量氧化剂的NaIO 4和AcOEt /（CH 3）2 CO / H 2 O（2：1：1，v / v / v）的双相溶剂体系。的1,5-二烯反应1，3，及5提供的新顺式-四氢呋喃产品2，4，6，和7具有完全的立体定向性。产品的结构是根据NMR和MS数据以及化学证据确定的。此过程以香叶基乙酸酯（中的应用8）和乙酸橙花酯（12得到）的顺式-四氢呋喃衍生物9，10，和13以高收率，并伴有少量的反式-tetrahydrofurandiols 11和14。这些产品与Sharpless等人获得的产品相同。RuO 4催化双相溶剂体系CCl 4中8和12的氧化/ CH 3 CN / H 2 O（2：2：3，v / v / v），但我们的方法具有立体特异性更高，材料回收率更高（约90％）和后处理更简单的优点。的1
• Oxidative cyclization of 5,6-dihydroxyalkenes promoted by Cr(VI) oxo species: A novel cis-2,5-disubstituted tetrahydrofuran synthesis
  作者：David M. Walba、George S. Stoudt

  DOI：10.1016/s0040-4039(00)86932-4

  日期：1982.1

  Oxidative cyclization of isomeric 5,6-dihydroxyalkenes of type derived from neryl and geranyl acetates with Cr(VI) oxo species afford cis-THF diols of type (syn addition across the double bond) with >99.5% stereospecificity.

  用Cr（VI）氧代物种衍生自乙酸甘油酯和香叶基乙酸酯的异构体5,6-二羟基烯烃的氧化环化反应提供顺式THF二醇类型（通过双键进行顺式加成），其立体专一性> 99.5％。
• A greatly improved procedure for ruthenium tetroxide catalyzed oxidations of organic compounds
  作者：Per H. J. Carlsen、Tsutomu Katsuki、Victor S. Martin、K. Barry Sharpless

  DOI：10.1021/jo00332a045

  日期：1981.9
• Total Synthesis of Thyrsiferyl 23-Acetate, a Specific Inhibitor of Protein Phosphatase 2A and an Anti-Leukemic Inducer of Apoptosis
  作者：Isabel C. González、Craig J. Forsyth

  DOI：10.1021/ja000001r

  日期：2000.9.1

  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.
• Perruthenate ion. Another metal oxo species able to promote the oxidative cyclisation of 1,5-dienes to 2,5-disubstituted cis -tetrahydrofurans
  作者：Vincenzo Piccialli、Teresa Caserta

  DOI：10.1016/j.tetlet.2003.10.173

  日期：2004.1

  Perruthenate ion, from tetrapropylammonium perruthenate (TPAP), in the presence of tetrabutylammonium periodate (TBAPI) as reoxidant catalyses the stereospecific and stereoselective oxidative cyclisation of 1,5-dienes to cis-2,5-disubstituted tetrahydrofurans in good to moderate yields. NMO also works as co-oxidant in the process but is less effective and at least 0.7 equiv TPAP are required. Acidic conditions promote the formation of THF diols. 1,5-Dienes with two terminal double bonds give poor yields of THF's or cleavage products. (C) 2003 Elsevier Ltd. All rights reserved.