(1S,2S)-2-hydroxy-1-methylcylopentanecarboxylic acid ethyl ester | 172825-22-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1S,2S)-2-hydroxy-1-methylcylopentanecarboxylic acid ethyl ester
• 英文别名: 1ref-Hydroxy-2cis-methyl-2trans-ethoxycarbonyl-cyclopentan；ethyl (1S,2S)-2-hydroxy-1-methylcyclopentane-1-carboxylate
• CAS: 172825-22-8
• 化学式: C₉H₁₆O₃
• 分子量: 172.224
• InChiKey: WXBAISPEXYPBPZ-CBAPKCEASA-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：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.89
• 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：

  (1S,2S)-2-hydroxy-1-methylcylopentanecarboxylic acid ethyl ester 在 咪唑 、 3,5-二甲基吡唑 、 chromium(VI) oxide 、 lithium aluminium tetrahydride 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 三乙胺 作用下， 以 乙醚 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 18.5h， 生成 (S)-4-(tert-Butyl-diphenyl-silanyloxymethyl)-4-methyl-cyclopent-2-enone
  参考文献：
  名称：

  Evaluation of possible intramolecular [4+2] cycloaddition routes for assembling the central tetracyclic core of the potent marine antiinflammatory agent mangicol A

  摘要：

  A plan for enantioselective construction of the mangicol A framework by means of intramolecular Diels-Alder cycloaddition is outlined. First to be assembled is the enantiopure cyclopentenecarboxylic acid 16. Of the several approaches targeting the 1,3-diene component 56, only that involving palladium-catalyzed enyne cyclization proved successful. Following the coupling of 16 to 56, we were unable to bring about any detectable level of (4 pi+2 pi) cycloaddition. Activation of the diene by incorporation of an OSiEt3 substituent on a terminal sp(2)-hybridized center likewise proved unsuccessful. Further facilitation was sought in the form of cyclopentenonecarboxylate 66. However, thermal activation, Lewis acid catalysis, and high-pressure conditions proved ineffective and did not lead to C-C bond formation. These studies serve to underscore the extent to which steric complications can complicate matters and the extent to which they must be skirted to arrive at the title compound. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2005.11.096
• 作为产物：
  描述：

  ethyl (S)-1-methyl-2-oxocyclopentane-1-carboxylate 在 二乙醇胺 、 (-)-diisopinocamphenylborane chloride 作用下， 生成 (1S,2S)-2-hydroxy-1-methylcylopentanecarboxylic acid ethyl ester
  参考文献：
  名称：

  Chiral Synthesis via Organoboranes. 43. Selective Reductions. 58. Reagent-Controlled Diastereoselective Reduction of (+)- and (−)-α-Chiral Ketones with (+)- and (−)-B-Chlorodiisopinocampheylborane

  摘要：

  Asymmetric reduction of (+)- and (-)-alpha-chiral ketones with (+)- and (-)-B-chlorodiisopinocampheylborane provides the product alcohols in very high diastereomeric excess, with the matched pairs providing >100:1 selectivity and the mismatched pairs showing 4:1-15:1 selectivity. The high selectivity achieved even in the mismatched pairs reveals the power of the reagent to control the stereochemical outcome. The rates of the reaction of the matched pairs are faster than those of the mismatched pairs, In all the cases studied thus far, the (-)-reagent ((d)Ipc(2)BCl) and (S)ketone or the (+)-reagent ((l)Ipc(2)BCl) and (R)-ketone constitute matched pairs and the (-)-reagent and (R)-ketone or the (+)-reagent and (S)-ketone constitute mismatched pairs, A possible mechanism for the reductions is discussed.

  DOI：

  10.1021/jo951207r

文献信息

• Synthesis and Neurotrophic Activity Studies of <i>Illicium</i> Sesquiterpene Natural Product Analogues
  作者：Johannes Richers、Alexander Pöthig、Eberhardt Herdtweck、Claudia Sippel、Felix Hausch、Konrad Tiefenbacher

  DOI：10.1002/chem.201605362

  日期：2017.3.2

  the carbon framework of (±)‐Merrilactone A and (±)‐Anislactone A/B on a gram scale. This has allowed access to a series of structural analogues by modification of the core structure, including variation of oxidation levels and alteration of functional groups. In total, 15 derivatives of the natural products have been synthesized and tested for their neurite outgrowth activities. Our studies indicate

  神经营养天然产物具有潜在的特权结构，可用于开发抗神经退行性疾病的治疗剂。但是，仅进行了很少的研究来研究常见的药效基序和结构-活性关系（SAR）。在这里，研究结构上更简单的the毛神经营养倍半萜类似物介绍了家庭。简洁的合成路线可实现以克为单位制备（±）‐Merrilactone A和（±）‐Anislactone A / B的碳骨架。这样就可以通过修改核心结构来获得一系列结构类似物，包括氧化水平的变化和官能团的变化。总共合成了15种天然产物的衍生物，并测试了它们的神经突向外生长活性。我们的研究表明，有希望的生物活性可以通过结构更简单的天然产物类似物保留，而这些类似物可以通过简单的合成途径获得。
• A New Synthesis of (−)-Frontalin, the Bark Beetle Pheromone
  作者：Yutaka Nishimura、Kenji Mori

  DOI：10.1002/(sici)1099-0690(199802)1998:2<233::aid-ejoc233>3.0.co;2-m

  日期：1998.2

  (−)-Frontalin [(1S,5R)-1,5-dimethyl-6,8-dioxabicyclo[3.2.1]- octane (1)] was synthesized from ethyl 2-oxocyclopentane-1-carboxylate (2) as the starting material. Baker′s yeast was used for the asymmetric reduction of 2 to 3. The S configuration at C-1 of 1 was generated by diastereoselective methylation of the dianion derived from 3 to give 4. The present process furnished about 10 g of 1 with enantiomeric

  (-)-Frontalin [(1S,5R)-1,5-二甲基-6,8-二氧杂双环[3.2.1]-辛烷 (1)] 是由 2-氧代环戊烷-1-羧酸乙酯 (2) 合成的起始材料。面包酵母用于不对称还原 2 到 3。1 的 C-1 处的 S 构型是通过衍生自 3 的二价阴离子的非对映选择性甲基化产生的，得到 4。本方法为约 10 g 的 1 提供对映异构体纯度 89.1% ee
• Enzymatic hydrolysis of 2,2-bis(acetoxymethyl)cycloalkanones, and its application to formal synthesis of(-)-malyngolide.
  作者：HIROSHI SUEMUNE、TETSUJI HARABE、ZHUO-FENG XIE、KIYOSHI SAKAI

  DOI：10.1248/cpb.36.4337

  日期：——

  Asymmetric hydrolysis of 2, 2-bis (acetoxymethyl) cyclopentanone (5) using biocatalysts and its application to a formal synthesis of (-)-malyngolide are described.For the asymmetric induction at the quaternary carbon of 5, cholinesterase from electric eel was found to be effective to afford the (+)-monoacetate (6)(90%ee).Compound (+)-6 was easily converted to the synthetic intermediate (28) for (-)-malyngolide.

  介绍了利用生物催化剂对 2，2-双（乙酰氧甲基）环戊酮（5）进行不对称水解，并将其应用于 (-)-malyngolide 的正式合成。在 5 的季碳上进行不对称诱导时，发现来自电鳗的胆碱酯酶能有效地生成 (+)- 单乙酸酯 (6)（90%ee）。
• Chiral Synthesis via Organoboranes. 42. Selective Reductions. 57. Efficient Kinetic Resolution of Representative α-Tertiary Ketones with <i>B</i>-Chlorodiisopinocampheylborane
  作者：P. Veeraraghavan Ramachandran、Guang-Ming Chen、Herbert C. Brown

  DOI：10.1021/jo951206z

  日期：1996.1.1

  Kinetic resolution of racemic alpha-tertiary ketones with 0.5-0.6 molar equiv of B-chlorodiisopinocampheylborane provides the product alcohols in very high diastereomeric and enantiomeric excess, with the unreacted ketone recovered in very high ee. For example, ethyl 1-methyl-8-oxocyclopentane- and -cyclohexanecarboxylates are partially reduced to recover the ketone in 91 greater than or equal to 99% ee and the product alcohols in up to 94% de, with >90% ee for the major diastereomer. Bicyclic ketones, such as 1-methyl- and 1-ethylnorcamphor, camphor, and camphenilone, are readily resolved to provide the ketone in 92 to greater than or equal to 99% ee, with the product alcohol recovered in high de and ee. Dihydrospiro[bicyclo[3.2.1]octane-2,2'(3'H)-furan]-3-one is resolved to provide the ketone in greater than or equal to 99% ee and the product alcohol in greater than or equal to 99% de. In all the cases studied, the R-isomer of the ketone is recovered when (d)Ipc(2)BCl is used for kinetic resolution, while (l)Ipc(2)BCl provides the S-ketone. Optimum conditions for obtaining the product alcohol, or the ketone, or both, in very high yields and ee have been established.
• Stereocontrolled cyclization reactions mediated by samarium diiodide
  作者：Gary A. Molander、Jeffrey B. Etter、Paul W. Zinke

  DOI：10.1021/ja00236a025

  日期：1987.1