(E,2R,3S)-3-hydroxy-2-methylhex-4-enoic acid | 131725-10-5

• 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: (E,2R,3S)-3-hydroxy-2-methylhex-4-enoic acid
• CAS: 131725-10-5
• 化学式: C₇H₁₂O₃
• 分子量: 144.17
• InChiKey: MOILFTNPYDAQJN-ZRKSVAJOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  10
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  57.5
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (E,2R,3S)-3-hydroxy-2-methylhex-4-enoic acid 在 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 反应 4.0h， 生成 3-(E)-(2S,3R)-2-methyl-4-hexene-1,3-diol
  参考文献：
  名称：

  Assignment of stereochemistry in the oligomycin/rutamycin/cytovaricin family of antibiotics. Asymmetric synthesis of the rutamycin spiroketal synthon

  摘要：

  The absolute stereochemistry of the rutamycin antibiotics 2a,b has been established through asymmetric synthesis of the known degradation product 4. One of the key steps in the assemblage process involves acylation of the metalated hydrazone 6 with the N-methoxy-N-methyl amide 5. Both of these enantiomerically pure intermediates have been prepared in good overall yield and high diastereoselectivity (de > 94%). All absolute stereochemical relationships were established through alkylation and aldol bond constructions using N-acyloxazolidinone chiral auxiliaries. Subjection of 17 to acid hydrolysis/deprotection resulted in loss of protecting groups and subsequent spiroketalization to 19 (80%). Silylation of the secondary alcohol in 19 was followed by a samarium-catalyzed Meerwein-Ponndorf-Verley reduction to provide the equatorial alcohol 20 in excellent yield and stereoselectivity (de = 97%). Control experiments indicate that this surprisingly stereoselective reaction operates under kinetic control and that the observed stereochemical outcome may be the result of coordination of the reactive reducing agent to the axial spiroketal oxygen. Conversion of 20 to triol 4 afforded material that is identical with the rutamycin degradation product in all respects. These results establish that the absolute stereochemistry of the rutamycins is as shown (2a,b).

  DOI：

  10.1021/jo00313a011
• 作为产物：
  描述：

  [(1R,2S)-2-[methyl(1,2,3,4,5,6,7,8-octahydroanthracen-9-ylsulfonyl)amino]-1-phenylpropyl] (E,2R,3S)-3-hydroxy-2-methylhex-4-enoate 生成 (E,2R,3S)-3-hydroxy-2-methylhex-4-enoic acid
  参考文献：
  名称：

  的程度顺式-选择性为羧酸酯的硼介导的不对称醛醇缩合反应

  摘要：

  为顺式选择性羟醛缩合反应的新的手性试剂已经被开发了基于最近的发现，即羧酸酯的硼介导的醛醇缩合反应的立体化学通过该酯的醇部分的膨松度的控制，通过适当选择试剂，并受烯醇化条件的影响。这种易于获得的廉价试剂已被用于大环内酯单萜内酯的合成研究中。

  DOI：

  10.1016/s0040-4039(98)00123-3

文献信息

• An Activated Germanium Metal-Promoted, Highly Diastereoselective Reformatsky Reaction
  作者：Hirotaka Kagoshima、Yukihiko Hashimoto、Dai Oguro、Kazuhiko Saigo

  DOI：10.1021/jo971672j

  日期：1998.2.1

  germanium(II) iodide with potassium metal, was found to promote the Reformatsky reaction effectively under mild conditions. In the presence of activated germanium metal, the reactions of alpha-bromo ketones 2a and 2b and alpha-bromo imides 2e and 2f with benzaldehyde (1a) proceeded smoothly to give the corresponding beta-hydroxy carbonyl compounds 3a, 3b, 3e and 3f, respectively, in good yields and with

  人们发现，在温和的条件下，通过用钾金属还原碘化锗（II）制备的活化锗金属可有效促进Reformatsky反应。在活化锗金属的存在下，α-溴代酮2a和2b以及α-溴代酰亚胺2e和2f与苯甲醛（1a）的反应顺利进行，得到相应的β-羟基羰基化合物3a，3b，3e和3f，分别具有良好的收率和良好的非对映选择性。还研究了对映体纯的恶唑烷酮衍生物2g-j与各种醛1a-d的活化的锗金属促进的不对称Reformatsky反应；当（1S，2R）-2-氨基-1,2-二苯乙醇衍生的2j被用作Reformatsky供体时，获得了最高的非对映选择性。极好的非对映选择性可以用齐默曼-特拉克斯勒模型中在醛和烯醇酸酯之间形成的椅子状六元过渡态来解释。Reformatsky加合物的一次重结晶，然后水解和随后的酯化反应，产生对映体纯的3-羟基-2-甲基链烷酸甲酯10j-m，几乎定量回收了对映体纯的2-恶唑烷酮14。
• Asymmetric aldol reactions: a novel model for switching between chelation- and non-chelation-controlled aldol reactions
  作者：Tu Hsin Yan、Chang Wei Tan、Hui Chun Lee、Hua Chi Lo、Tzung Yu Huang

  DOI：10.1021/ja00060a010

  日期：1993.4

  A new camphor-based N-propionyloxazolidinethione provides remarkable levels of asymmetric induction for both chelation-and non-chelation-controlled aldol processes. While the aldol condensation of the derived di-n-butylboryl enolate with various aldehydes affords the 'Evans'' syn aldol with excellent diastereoselectivity, the chlorotitanium enolate gives the ''non-Evans' syn aldol expected from chelation control. Most noteworthy is the observation that the sense of facial selectivity from the chlorotitanium enolate of propionyloxazolidinethione is opposite to that obtained from propionyloxazolidinone. This important finding illustrates the importance of increased chelating potential of the enolate ligand, ring thiocarbonyl, in maximizing the aldol pi-facial discrimination. Final nondestructive chiral auxiliary removal via hydroperoxide-assisted hydrolysis and subsequent esterification provides enantiomerically pure methoxy-carbonyl aldols.
• HEATHCOCK, CLAYTON H.;FINKELSTEIN, BRUCE L.;JARVI, ESA T.;RADEL, PEGGY A.+, J. ORG. CHEM., 53,(1988) N 9, 1922-1942
  作者：HEATHCOCK, CLAYTON H.、FINKELSTEIN, BRUCE L.、JARVI, ESA T.、RADEL, PEGGY A.+

  DOI：——

  日期：——
• Assignment of stereochemistry in the oligomycin/rutamycin/cytovaricin family of antibiotics. Asymmetric synthesis of the rutamycin spiroketal synthon
  作者：David A. Evans、Dale L. Rieger、Todd K. Jones、Stephen W. Kaldor

  DOI：10.1021/jo00313a011

  日期：1990.12

  The absolute stereochemistry of the rutamycin antibiotics 2a,b has been established through asymmetric synthesis of the known degradation product 4. One of the key steps in the assemblage process involves acylation of the metalated hydrazone 6 with the N-methoxy-N-methyl amide 5. Both of these enantiomerically pure intermediates have been prepared in good overall yield and high diastereoselectivity (de > 94%). All absolute stereochemical relationships were established through alkylation and aldol bond constructions using N-acyloxazolidinone chiral auxiliaries. Subjection of 17 to acid hydrolysis/deprotection resulted in loss of protecting groups and subsequent spiroketalization to 19 (80%). Silylation of the secondary alcohol in 19 was followed by a samarium-catalyzed Meerwein-Ponndorf-Verley reduction to provide the equatorial alcohol 20 in excellent yield and stereoselectivity (de = 97%). Control experiments indicate that this surprisingly stereoselective reaction operates under kinetic control and that the observed stereochemical outcome may be the result of coordination of the reactive reducing agent to the axial spiroketal oxygen. Conversion of 20 to triol 4 afforded material that is identical with the rutamycin degradation product in all respects. These results establish that the absolute stereochemistry of the rutamycins is as shown (2a,b).
• Attainment of syn-selectivity for boron-mediated asymmetric aldol reactions of carboxylic esters
  作者：Ji-Feng Liu、Atsushi Abiko、Zhonghua Pei、Dana C Buske、Satoru Masamune

  DOI：10.1016/s0040-4039(98)00123-3

  日期：1998.4

  reagent for syn-selective aldol reactions has been developed based on the recent finding that the stereochemistry of the boron-mediated aldol reaction of a carboxylic ester is controlled by the bulkiness of the alcohol moiety of the ester, by the proper choice of reagents, and by the enolization conditions. This readily available, inexpensive reagent has been utilized in studies directed towards the synthesis

  为顺式选择性羟醛缩合反应的新的手性试剂已经被开发了基于最近的发现，即羧酸酯的硼介导的醛醇缩合反应的立体化学通过该酯的醇部分的膨松度的控制，通过适当选择试剂，并受烯醇化条件的影响。这种易于获得的廉价试剂已被用于大环内酯单萜内酯的合成研究中。