Ethyl (3S,5S)-3-hydroxy-5,6-(isopropylidenedioxy)hexanoate | 91312-54-8

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羟基酸及其衍生物
• 英文名称: Ethyl (3S,5S)-3-hydroxy-5,6-(isopropylidenedioxy)hexanoate
• 英文别名: ethyl (3S,5S)-5,6-O-isopropylidene-3,5,6-trihydroxyhexanoate；ethyl (3S,5S)-5,6-(isopropylidenedioxy)-3-hydroxyhexanoate；ethyl (3S)-4-[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]-3-hydroxybutanoate
• CAS: 91312-54-8
• 化学式: C₁₁H₂₀O₅
• 分子量: 232.277
• InChiKey: YDNZMIOIJMCEMQ-IUCAKERBSA-N

物化性质

• 沸点：
  330.8±22.0 °C(Predicted)
• 密度：
  1.084±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.4
• 重原子数：
  16
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  65
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  Ethyl (3S,5S)-3-hydroxy-5,6-(isopropylidenedioxy)hexanoate 在 咪唑 、 六甲基磷酰三胺 、 4-二甲氨基吡啶 、 正丁基锂 、 4-甲基苯磺酸吡啶 、 sodium hydride 、 lithium diisopropyl amide 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 97.5h， 生成 Methyl (1R(1'E,3'E,5'E),2S,3S,5S)-3-O-(tert-butyldiphenylsilyl)-1-(1',5'-dimethyl-6'-(2-methyloxazol-4-yl)-1',3',5'-hexatrienyl)-2-methyl-2,4-dideoxymannopyranoside
  参考文献：
  名称：

  Synthesis of the lower subunit of rhizoxin

  摘要：

  Full details of a study leading to a synthesis of the optically active C13-C26 lower subunit of rhizoxin including the side-chain chromophore characteristic of the full class of antimitotic agents are described. A key element of the synthesis is the stereoselective introduction of the C18-C19 trisubstituted olefin through use of a Wadsworth-Horner-Emmons condensation of 3 with beta-keto phosphonate 38 bearing resident functionality suitable for the diastereoselective introduction of C15-C17 employing a hydroxyl-directed reduction of the resultant beta-hydroxy ketone.

  DOI：

  10.1021/jo00034a010
• 作为产物：
  描述：

  (S)-4-(2-羟乙基)-2,2-二甲基-1,3-二氧戊环 在 aluminum amalgam 、 草酰氯 、 叔丁基氯化镁 、 二甲基亚砜 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 为溶剂， 反应 25.25h， 生成 Ethyl (3S,5S)-3-hydroxy-5,6-(isopropylidenedioxy)hexanoate
  参考文献：
  名称：

  Bakers' yeast oxidation of methyl para-tolylsuifide: Synthesis of a chiral intermediate in the preparation of the mevinic acid-type hypocholestemic agents

  摘要：

  The use of (R)-methyl para-tolylsulfoxide as a chiral auxiliary in a novel synthesis of a key intermediate en route to mevinic acid-type hypocholestemic agents is described. The synthesis is short and simple consisting of eight steps to yield enantiomerically pure beta-silyloxy-delta-lactone. The chiral sulfoxide used in the synthesis was obtained via a straightforward biooxidation of methyl paratolylsulfide using bakers' yeast (Saccharomyces cerevisiae NCYC 73). The biotransformation involves the use of whole cells and affords the sulfoxide in good yield and with high stereoselectivity.

  DOI：

  10.1016/0040-4020(95)00819-t

文献信息

• Enantioselective Formal Hydration of α,β-Unsaturated Imides by Al-Catalyzed Conjugate Addition of Oxime Nucleophiles
  作者：Christopher D. Vanderwal、Eric N. Jacobsen

  DOI：10.1021/ja045563f

  日期：2004.11.1

  (salen)Al-catalyzed asymmetric conjugate addition of salicylaldoxime to α,β-unsaturated imides is the key step in an efficient and highly enantioselective two-step formal hydration of these electron-deficient olefins. This reaction constitutes the first example of an enantioselective conjugate addition of an oxygen-centered nucleophile to α,β-unsaturated carboxylic acid derivatives. Application of this method

  (salen)Al 催化的水杨醛肟与 α,β-不饱和酰亚胺的不对称共轭加成是这些缺电子烯烃高效且高度对映选择性的两步形式水合的关键步骤。该反应构成了以氧为中心的亲核试剂与 α,β-不饱和羧酸衍生物的对映选择性共轭加成的第一个例子。将该方法应用于手性非外消旋底物显示出高水平的催化剂诱导的非对映选择性，强调了其在聚酮化合物天然产物合成中的潜在用途。
• Highly stereoselective hydrogenations-As key-steps in the total synthesis of statins
  作者：Natalia Andrushko、Vasyl Andrushko、Vitali Tararov、Andrei Korostylev、Gerd König、Armin Börner

  DOI：10.1002/chir.20782

  日期：2010.5.15

  Statins are inhibitors of 3‐hydroxy‐3‐methyl‐glutaryl coenzyme A reductase (HMG‐CoA reductase) and became the standard of care for treatment of hypercholesterolemia because of their efficacy, safety, and long‐term benefits. They are administered as diastereo‐ and enantiomerically pure compounds. We summarize here two new approaches for the total synthesis of the most important representatives, atorvastatin

  他汀类药物是3-羟基-3-甲基戊二酰辅酶A还原酶（HMG-CoA还原酶）的抑制剂，由于其功效，安全性和长期益处，已成为治疗高胆固醇血症的护理标准。它们以非对映体和对映体纯化合物的形式给药。我们在此总结了两种新方法，这些方法以高度立体选择性氢化为关键步骤，用于总合成最重要的代表阿托伐他汀和瑞舒伐他汀。手性2010。©2009 Wiley‐Liss，Inc.。
• Synthesis and Highly Stereoselective Hydrogenation of the Statin Precursor Ethyl (5S)-5,6-Isopropylidenedioxy-3-oxohexanoate
  作者：Vitali I. Tararov、Gerd König、Armin Börner

  DOI：10.1002/adsc.200600291

  日期：2006.12

  -oxohexanoates (2) – a key intermediate in the synthesis of pharmacologially important statins – starting from (S)-malic acid is described. The synthesis of the required initial compound methyl (3S)-3,4-(isopropylidenedioxy)butanoate (1) by Moriwake’s reduction of dimethyl (S)-malate (3) has been improved. Direct 2-C chain elongation of ester 1 using the lithium enolate of tert-butyl acetate has been

  描述了从（S）-苹果酸开始大规模制备（5 S）-5,6-（异丙基二烯二氧基）-3-氧己酸（2）-合成重要的他汀类药物的关键中间体的尝试。 。所需的初始化合物甲基（3所述的合成小号）-3,4-（异亚丙二）丁酸甲酯（1）由守分的还原二甲酯（小号） -苹果（3）进行了改进。已显示使用乙酸叔丁酯的烯醇锂将酯1直接2-C链延长是烯醇化物过量3至5倍的成功方法。不幸的是，该产品叔丁基（5蒸馏期间，S）-5，6-（异丙基二烯二氧基）-3-氧己酸酯（2a）不稳定。（5 S）-5,6-（异丙基二烯氧基）-3-氧己酸乙酯（2b）可以用N活化，从（3 S）-3,4-（异丙基二烯氧基）丁酸（7）以克数制得。 N'-羰基二咪唑及随后与Mg（OOCCH 2 COOEt）2的反应。还描述了原位制备后者的便利途径。乙酯（2b）可以有利地通过蒸馏纯化。β-酮酸酯催化加氢的立体化学（2b）合成了许多均相的非手性和手性Rh（I）和Ru（II）配合物，合成了（5
• Synthesis of the lower subunit of rhizoxin
  作者：Dale L. Boger、Timothy T. Curran

  DOI：10.1021/jo00034a010

  日期：1992.4

  Full details of a study leading to a synthesis of the optically active C13-C26 lower subunit of rhizoxin including the side-chain chromophore characteristic of the full class of antimitotic agents are described. A key element of the synthesis is the stereoselective introduction of the C18-C19 trisubstituted olefin through use of a Wadsworth-Horner-Emmons condensation of 3 with beta-keto phosphonate 38 bearing resident functionality suitable for the diastereoselective introduction of C15-C17 employing a hydroxyl-directed reduction of the resultant beta-hydroxy ketone.
• Bakers' yeast oxidation of methyl para-tolylsuifide: Synthesis of a chiral intermediate in the preparation of the mevinic acid-type hypocholestemic agents
  作者：Jenny Tang、Ian Brackenridge、Stanley M. Roberts、Jean Beecher、Andrew J. Willetts

  DOI：10.1016/0040-4020(95)00819-t

  日期：1995.11

  The use of (R)-methyl para-tolylsulfoxide as a chiral auxiliary in a novel synthesis of a key intermediate en route to mevinic acid-type hypocholestemic agents is described. The synthesis is short and simple consisting of eight steps to yield enantiomerically pure beta-silyloxy-delta-lactone. The chiral sulfoxide used in the synthesis was obtained via a straightforward biooxidation of methyl paratolylsulfide using bakers' yeast (Saccharomyces cerevisiae NCYC 73). The biotransformation involves the use of whole cells and affords the sulfoxide in good yield and with high stereoselectivity.