(2R,3E)-2-(hydroxymethyl)-5-methylhex-3-enyl acetate | 155489-75-1

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (2R,3E)-2-(hydroxymethyl)-5-methylhex-3-enyl acetate
• 英文别名: (S)-(E)-2-(Acetoxymethyl)-5-methylhex-3-en-1-ol；[(E,2R)-2-(hydroxymethyl)-5-methylhex-3-enyl] acetate
• CAS: 155489-75-1
• 化学式: C₁₀H₁₈O₃
• 分子量: 186.251
• InChiKey: YHTFPDPIIMMIBU-ORAHPGNNSA-N

物化性质

• 沸点：
  244.1±28.0 °C(Predicted)
• 密度：
  0.985±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  13
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2R,3E)-2-(hydroxymethyl)-5-methylhex-3-enyl acetate 在 咪唑 、 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) 、 sodium azide 、 Pseudomonas capacia 、 四丁基氟化铵 、 水 、 sodium hydride 、 三乙胺 、 间氯过氧苯甲酸 、 三苯基膦 作用下， 以 四氢呋喃 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 生成 (5R)-5-hydroxymethyl-7-oxa-3-azabicyclo[4.1.0]heptane-3-carboxylic acid tert-butyl ester
  参考文献：
  名称：

  Asymmetrized tris(hydroxymethyl)methane as precursor of iminosugars: application to the synthesis of isofagomine

  摘要：

  A new synthetic application of asymmetrized tris(hydroxymethyl)methane (THYM*), readily obtained in both enantiomeric forms through a chemoenzymatic procedure, is reported. In this case THYM* precursor 3 was elaborated by ring closing metathesis into some enantiopure branched tetrahydropyridines, that hake been used as precursors of the potent glycosidase inhibitor isofagomine 28. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(02)02492-9
• 作为产物：
  描述：

  (E)-2-(3-methyl-1-buten-1-yl)-1,3-propanediol 在 吡啶 作用下， 以 水 、 异丙醇 为溶剂， 反应 6.0h， 生成 (2R,3E)-2-(hydroxymethyl)-5-methylhex-3-enyl acetate
  参考文献：
  名称：

  Chemoenzymic preparation of asymmetrized tris(hydroxymethyl)methane (THYM*) and of asymmetrized bis(hydroxymethyl)acetaldehyde (BHYMA*) as new highly versatile chiral building blocks

  摘要：

  A series of asymmetrized tris(hydroxymethyl)methanes 2 and bis(hydroxymethyl)acetaldehydes 3 have been prepared in both enantiomeric forms through a chemoenzymatic methodology. The key step is the highly enantioselective PPL-catalyzed monohydrolysis of 2(E)-alkenyl-1,3-diacetoxypropanes 25-27. A careful study on the effect of unsaturations adjacent to the prochiral center in a series of 2-substituted 1,3-diacetoxypropanes has confirmed the suggested beneficial effect of a pi-system in that position but has also unveiled an unprecedented dramatic effect of double-bond configuration on enantioselectivity. A new empirical model for the interpretation of these and other results, based both on polarity and steric arguments, is proposed. This study provides a general protocol for the efficient synthesis of asymmetrized 1,3-propanediols bearing in position 2 saturated or unsaturated carbon chains.

  DOI：

  10.1021/jo00031a039

文献信息

• On the optimization of pig pancreatic lipase catalyzed monoacetylation of prochiral diols
  作者：Luca Banfi、Giuseppe Guanti、Renata Riva

  DOI：10.1016/0957-4166(95)00167-n

  日期：1995.6

  The effect of various experimental variables (solvent, methodology of supportation on celite, presence of water, conversion and so on) on the rate and on the enantioselectivity of monoacetylation of some prochiral 2-substituted-1,3-propanediols with vinyl acetate catalyzed by crude PPL (pig pancreatic lipase) was analyzed. This study allowed to assess the best conditions for performing these transformations

  各种实验变量（溶剂，对硅藻土的支持方法，水的存在，转化率等）对某些前手性2-取代-1,3-丙二醇与醋酸乙烯酯催化的单手性2-取代-1,3-丙二醇单乙酰化的速率和对映选择性的影响分析了粗PPL（猪胰脂肪酶）。这项研究可以评估执行这些转化的最佳条件，从而为合成有价值的手性结构单元提供了一种有效的方法，其中含有适量的廉价PPL，这些PPL也可以轻松地回收利用。
• Diversity oriented and chemoenzymatic synthesis of densely functionalized pyrrolidines through a highly diastereoselective Ugi multicomponent reaction
  作者：Valentina Cerulli、Luca Banfi、Andrea Basso、Valeria Rocca、Renata Riva

  DOI：10.1039/c1ob06632c

  日期：——

  A highly diastereoselective Ugi reaction involving a chiral cyclic imine, two enantiomerically pure isocyanides and various carboxylic acids was employed for the synthesis of polyfunctionalized pyrrolidines. Both chiral substrates have been efficiently prepared by chemoenzymatic methodologies from readily available achiral substrates. This highly convergent approach can find an application in the fragment-based

  涉及手性环状亚胺，两种对映体纯的异氰酸酯和各种羧酸的高度非对映选择性的Ugi反应用于合成多官能化吡咯烷。两种手性底物已经通过化学酶学方法从容易获得的非手性底物中有效地制备。这种高度收敛的方法可以在基于片段的药物发现过程中找到应用。
• Convergent synthesis of a key intermediate for hypocholesterolemic agent 1233A, starting from methyl 3-hydroxy-2-methylpropanoate and asymmetrized bis(hydroxymethyl)acetaldehyde (BHYMA*)
  作者：Giuseppe Guanti、Luca Banfi、Giovanna Schmid

  DOI：10.1016/s0040-4039(00)73162-5

  日期：1994.6

  Compound 2, which is a known intermediate for the total synthesis of hypocholesterolemic agent 1233A 1, has been synthesized in good overall yield through a convergent approach, employing 3-hydroxy-2-methylpropanoate 6 and BHYMA* 5 as chiral building blocks.

  化合物2是降胆固醇药1233A 1的总合成的已知中间体，已通过收敛方法以3-羟基-2-甲基丙酸酯6和BHYMA * 5为手性结构单元以高收率合成了化合物2 。
• Asymmetrized tris(hydroxymethyl)methane as a precursor of N- and O-containing 6-membered heterocycles through ring-closing metathesis
  作者：Luca Banfi、Giuseppe Guanti、Monica Paravidino、Renata Riva

  DOI：10.1039/b502952j

  日期：——

  A novel synthetic application of asymmetrized tris(hydroxymethyl)methane (THYM*) 1, obtained in both enantiomeric forms in high e.e. via a chemoenzymatic procedure, is described. Starting from the common precursor 3, N- and O-containing 6-membered heterocycles have been prepared exploiting ring-closing metathesis as the key step. Possible elaborations of the double bond in 6 and 28 have been explored and, in the case of 28, conversion into the glycosidase inhibitor isofagomine 53 has been achieved.

  描述了一种新颖的合成应用，即不对称三（羟甲基）甲烷（THYM*）1，采用化学酶法合成获得两种对映异构体，具有较高的对映体富集度。以常见前体3为起始材料，利用环闭合重排作为关键步骤合成了含氮和含氧的六元杂环。探讨了对6和28中双键的可能改造，在28的情况下，成功转化为糖苷酶抑制剂异伐果明53。
• Synthesis of enantiopure 2-carba-cyclic phosphatidic acid and effects of its chirality on biological functions
  作者：Emi Nozaki、Mari Gotoh、Harumi Hotta、Shuwa Hanazawa、Susumu Kobayashi、Kimiko Murakami-Murofushi

  DOI：10.1016/j.bbalip.2011.01.003

  日期：2011.4

  several metabolically stabilized derivatives of cPA. 2-Carba-cPA (2ccPA) is one of the synthesized compounds in which the phosphate oxygen was replaced with a methylene group at the sn-2 position, and it showed much more potent biological activities than natural cPA. Here, we developed a new method of 2ccPA enantiomeric synthesis. And we examined the effects of 2ccPA enantiomers on autotaxin (ATX) activity

  环状磷脂酸（cPA）是天然存在的磷脂介体，在甘油骨架的sn-2和sn-3位置具有一个非常独特的环状磷酸酯环。我们已经设计并化学合成了几种代谢稳定的cPA衍生物。2-Carba-cPA（2ccPA）是合成的化合物之一，其中磷酸氧在sn-2位置被亚甲基取代，并且比自然cPA具有更强的生物学活性。在这里，我们开发了一种2ccPA对映体合成的新方法。我们检查了2ccPA对映异构体对自分泌运动素（ATX）活性，癌细胞侵袭和伤害感受反射的影响。除消旋体2ccPA以外，两种对映体均显示出对ATX活性，癌细胞侵袭和伤害感受反射的抑制作用。