ethyl (4R,5S)-5-hydroxy-4-methylhex-2-enoate | 342900-84-9

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: ethyl (4R,5S)-5-hydroxy-4-methylhex-2-enoate
• 英文别名: ethyl (2E,4R,5S)-5-hydroxy-4-methylhex-2-enoate；ethyl (E,4R,5S)-5-hydroxy-4-methylhex-2-enoate
• CAS: 342900-84-9
• 化学式: C₉H₁₆O₃
• 分子量: 172.224
• InChiKey: SNMNXYHMRNFYDS-KTERXBQFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 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 (4R,5S)-5-hydroxy-4-methylhex-2-enoate 在 palladium dihydroxide potassium tert-butylate 、 氢气 作用下， 以 四氢呋喃 、 乙醇 为溶剂， 23.0 ℃ 、101.33 kPa 条件下， 反应 36.33h， 生成 (4S,5S,6S)-3,4,5,6-tetrahydro-4-hydroxy-5,6-dimethyl-2H-pyran-2-one
  参考文献：
  名称：

  Asymmetric Synthesis of the C(33) - C(37) Fragment of Amphotericin B

  摘要：

  We have devised an expeditious. efficient, asymmetric synthesis of the C(33)-C(37) fragment of amphotericin B that proceeds in 14 steps and 16% overall yield from tiglic aldehyde ((E)-2-methylbut-2-enal) with complete stereocontrol. The route described herein relies on the application of recently developed methods in catalytic asymmetric synthesis for stereocontrol through enantio- and diastereoselective functionalization of a substituted sorbate derivative.

  DOI：

  10.1002/1522-2675(20010321)84:3<613::aid-hlca613>3.0.co;2-4
• 作为产物：
  描述：

  ethyl (2E,4E)-4-methylhexa-2,4-dienoate 在 potassium osmate(VI) 、 tris-(dibenzylideneacetone)dipalladium(0) 、 potassium hexacyanoferrate(III) 吡啶 、 甲酸 、 三丁基膦 、 甲基磺酰胺 、 sodium hydride 、 potassium carbonate 、 氢化奎尼定 1,4-(2,3-二氮杂萘)二醚 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 、 乙腈 、 叔丁醇 为溶剂， 反应 105.0h， 生成 ethyl (4R,5S)-5-hydroxy-4-methylhex-2-enoate
  参考文献：
  名称：

  Asymmetric Synthesis of the C(33) - C(37) Fragment of Amphotericin B

  摘要：

  We have devised an expeditious. efficient, asymmetric synthesis of the C(33)-C(37) fragment of amphotericin B that proceeds in 14 steps and 16% overall yield from tiglic aldehyde ((E)-2-methylbut-2-enal) with complete stereocontrol. The route described herein relies on the application of recently developed methods in catalytic asymmetric synthesis for stereocontrol through enantio- and diastereoselective functionalization of a substituted sorbate derivative.

  DOI：

  10.1002/1522-2675(20010321)84:3<613::aid-hlca613>3.0.co;2-4

文献信息

• Iron-Catalyzed Regio- and Stereoselective Substitution of γ,δ-Epoxy-α,β-unsaturated Esters and Amides with Grignard Reagents
  作者：Takeshi Hata、Rie Bannai、Mamoru Otsuki、Hirokazu Urabe

  DOI：10.1021/ol100022w

  日期：2010.3.5

  When γ,δ-epoxy-α,β-unsaturated esters or amides were treated with 2 equiv of Grignard reagents in the presence of 10−24 mol % FeCl2, regio- and stereoselective substitution of the epoxide moiety with the Grignard reagent occurred to give exclusively δ-hydroxy-γ-alkyl or aryl-α,β-unsaturated esters or amides in good yields.

  当在10−24 mol％FeCl 2存在下用2当量的Grignard试剂处理γ，δ-环氧-α，β-不饱和酯或酰胺时，发生了用Grignard试剂对环氧部分进行区域和立体选择性取代仅以高收率得到δ-羟基-γ-烷基或芳基-α，β-不饱和酯或酰胺。
• Ruthenium-Catalyzed Enyne Cycloisomerizations. Effect of Allylic Silyl Ether on Regioselectivity
  作者：Barry M. Trost、Jean-Philippe Surivet、F. Dean Toste

  DOI：10.1021/ja046824o

  日期：2004.12.1

  Ruthenium catalysts effect efficiently such single-step cycloisomerization at room temperature in acetone under neutral conditions. The cycloisomerization functions with (E) or (Z) 1,2-disubstituted alkenes. Parameters influencing the enol silane geometry are discussed. The level of selectivity depends on the alkyne substitution, the geometry of the double bond, and the nature of the catalyst. Furthermore

  1,6- 和 1,7-烯炔在末端烯丙基位置被叔丁基二甲基甲硅烷基醚基团取代的钌催化环异构化成为形成前所未有的具有几何定义烯醇硅烷的五元或六元环的有效反应. 介绍了对各种非手性 1,6- 和 1,7- 烯炔以及手性烯炔的直接合成途径。钌催化剂在中性条件下在丙酮中在室温下有效地实现这种单步环异构化。环异构化作用与 (E) 或 (Z) 1,2-二取代烯烃。讨论了影响烯醇硅烷几何形状的参数。选择性的水平取决于炔烃取代、双键的几何形状和催化剂的性质。此外，
• Asymmetric Synthesis of the C(33) - C(37) Fragment of Amphotericin B
  作者：Joakim Tholander、Erick M. Carreira

  DOI：10.1002/1522-2675(20010321)84:3<613::aid-hlca613>3.0.co;2-4

  日期：2001.3.21

  We have devised an expeditious. efficient, asymmetric synthesis of the C(33)-C(37) fragment of amphotericin B that proceeds in 14 steps and 16% overall yield from tiglic aldehyde ((E)-2-methylbut-2-enal) with complete stereocontrol. The route described herein relies on the application of recently developed methods in catalytic asymmetric synthesis for stereocontrol through enantio- and diastereoselective functionalization of a substituted sorbate derivative.