Ethyl (3R*,4S*)-(+/-)-3-hydroxy-2,4-dimethylpent-4-enoate | 92207-76-6

• 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 (3R*,4S*)-(+/-)-3-hydroxy-2,4-dimethylpent-4-enoate
• 英文别名: ethyl(S^*,S^*)-2,4-dimethyl-3-hydroxy-4-hexenoate；ethyl (2S,3R)-3-hydroxy-2,4-dimethylpent-4-enoate
• CAS: 92207-76-6
• 化学式: C₉H₁₆O₃
• 分子量: 172.224
• InChiKey: UPTOZGCPFGFQFI-YUMQZZPRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  12
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 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：

  Ethyl (3R*,4S*)-(+/-)-3-hydroxy-2,4-dimethylpent-4-enoate 在 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 以83%的产率得到(2R*,3R*)-(+/-)-2,4-Dimethylpent-4-en-1,3-diol
  参考文献：
  名称：

  Breit, Bernhard; Zahn, Stephan K., Tetrahedron Letters, 1998, vol. 39, # 14, p. 1900 - 1904

  摘要：

  DOI：
• 作为产物：
  描述：

  Ethyl (+/-)-3-hydroxy-4-methyl-4-pentenoate 、 碘甲烷 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 正己烷 、 六甲基磷酰三胺 为溶剂， 反应 0.58h， 以85%的产率得到Ethyl (3R*,4S*)-(+/-)-3-hydroxy-2,4-dimethylpent-4-enoate
  参考文献：
  名称：

  Substrate-Directed Diastereoselective Hydroformylation: Key Step for the Assembly of Polypropionate Subunits

  摘要：

  Stereoselective hydroformylation of methallylic alcohols of types 3 and 4, that employed the substrate-bound catalyst-directing ortho-diphenyl-phosphanylbenzoyl (o-DPPB) group, was used as a key step for the construction of bifunctionalized stereotriads, which ale central building blocks of polyketide natural products. The required diastereomerically pure syn- and anti- starting methallylic alcohol systems 3 and 4 were obtained either by Cram-selective carbonyl reduction, Frater alkylation, or by chelation-controlled carbonyl reduction. Enantiomerically pure stereotriad building blocks were derived from a combination of an Evans aldol addition and subsequent o-DPPB-directed stereoselective hydroformylation (-->24). A crystal structure analysis for steretriad building block 24 confirmed the relative and absolute configuration of the stereogenic centers. Additionally, it provided evidence for a previously postulated preferred conformation of the catalyst-directing o-DPPB group as well as of the polyketide main chain.

  DOI：

  10.1002/(sici)1521-3765(19991001)5:10<2819::aid-chem2819>3.0.co;2-z

文献信息

• The stereoselective α-alkylation of chiral β-hydroxy esters and some applications thereof
  作者：G. Fráter、U. Müller、W. Günther

  DOI：10.1016/s0040-4020(01)82413-3

  日期：1984.1

  The stereoselectivity of the α-alkylation of chiral β-hydroxy ester is discussed. The configuration of the alkylated product was proved chemically (Scheme 2). A one pot aldol-alkylation reaction was developed leading stereoselectively to racemic (s*,s*)-α-alkyl-β-hydroxy ester (Scheme 3,4). Baker's yeast reduction of 2-alkyl-3-keto ester led to valuable chiral (2RS,3S)-intermediates, which were converted

  讨论了手性β-羟基酯的α-烷基化的立体选择性。通过化学方法证明了烷基化产物的构型（方案2）。进行了一锅羟醛烷基化反应，立体选择性地生成了外消旋（s *，s *）-α-烷基-β-羟基酯（方案3,4）。贝克的2-烷基-3-酮酯的酵母还原反应产生了有价值的手性（2 RS，3 S）中间体，该中间体通过相应的二价阴离子转化为具有手性季C原子的化合物（方案6）。上述发现的合成应用显示在各种手性化合物的合成中（方案8和9）。
• Breit, Bernhard; Zahn, Stephan K., Tetrahedron Letters, 1998, vol. 39, # 14, p. 1900 - 1904
  作者：Breit, Bernhard、Zahn, Stephan K.

  DOI：——

  日期：——
• Breit, Bernhard, Angewandte Chemie, 1996, vol. 108, # 23/24, p. 3021 - 3023
  作者：Breit, Bernhard

  DOI：——

  日期：——
• Substrate-Directed Diastereoselective Hydroformylation: Key Step for the Assembly of Polypropionate Subunits
  作者：Bernhard Breit、Mario Dauber、Klaus Harms

  DOI：10.1002/(sici)1521-3765(19991001)5:10<2819::aid-chem2819>3.0.co;2-z

  日期：1999.10.1

  Stereoselective hydroformylation of methallylic alcohols of types 3 and 4, that employed the substrate-bound catalyst-directing ortho-diphenyl-phosphanylbenzoyl (o-DPPB) group, was used as a key step for the construction of bifunctionalized stereotriads, which ale central building blocks of polyketide natural products. The required diastereomerically pure syn- and anti- starting methallylic alcohol systems 3 and 4 were obtained either by Cram-selective carbonyl reduction, Frater alkylation, or by chelation-controlled carbonyl reduction. Enantiomerically pure stereotriad building blocks were derived from a combination of an Evans aldol addition and subsequent o-DPPB-directed stereoselective hydroformylation (-->24). A crystal structure analysis for steretriad building block 24 confirmed the relative and absolute configuration of the stereogenic centers. Additionally, it provided evidence for a previously postulated preferred conformation of the catalyst-directing o-DPPB group as well as of the polyketide main chain.