(1R,2R,1S')-1-ethoxycarbonyl-1-methyl-2-(1',2'-dihydroxyethyl)cyclopropane | 258821-59-9

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (1R,2R,1S')-1-ethoxycarbonyl-1-methyl-2-(1',2'-dihydroxyethyl)cyclopropane
• 英文别名: ethyl (1R,2R)-2-[(1S)-1,2-dihydroxyethyl]-1-methylcyclopropane-1-carboxylate
• CAS: 258821-59-9
• 化学式: C₉H₁₆O₄
• 分子量: 188.224
• InChiKey: AOXZYNYXZNAQPY-LKEWCRSYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.1
• 重原子数：
  13
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  66.8
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (1R,2R,1S')-1-ethoxycarbonyl-1-methyl-2-(1',2'-dihydroxyethyl)cyclopropane 在 ruthenium(IV) oxide 、 sodium perchlorate 、 氯甲酸乙酯 作用下， 生成 ethyl 2-azidocarbonyl-1-methyl-(1R,2R)-cyclopropane-1-carboxylate
  参考文献：
  名称：

  二苯基脯氨醇甲硅烷基醚催化α-取代的α,β-烯醛的不对称硝基环丙烷化用于构建全碳四元立体中心

  摘要：

  发现二苯基脯氨醇甲硅烷基醚介导的 α-取代的 α,β-不饱和醛与溴硝基甲烷的不对称硝基环丙烷化，然后是碱促进的异构化，可提供具有全碳四元立体中心的反式硝基环丙烷甲醛，具有优异的非对映选择性和对映选择性。DFT 计算表明亚胺离子中间体的 s-反式构象异构体比 s-顺式构象异构体更稳定。此外，计算出溴硝基甲烷阴离子对亚胺离子中间体的亲核攻击优先发生在吡咯烷亚胺中间体的大取代基的相反侧。

  DOI：

  10.1002/ejoc.201500838
• 作为产物：
  描述：

  ethyl 3-[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]-2-methylprop-2-enoate 在 盐酸 作用下， 以 乙醇 、 水 为溶剂， 生成 (1R,2R,1S')-1-ethoxycarbonyl-1-methyl-2-(1',2'-dihydroxyethyl)cyclopropane
  参考文献：
  名称：

  二苯基脯氨醇甲硅烷基醚催化α-取代的α,β-烯醛的不对称硝基环丙烷化用于构建全碳四元立体中心

  摘要：

  发现二苯基脯氨醇甲硅烷基醚介导的 α-取代的 α,β-不饱和醛与溴硝基甲烷的不对称硝基环丙烷化，然后是碱促进的异构化，可提供具有全碳四元立体中心的反式硝基环丙烷甲醛，具有优异的非对映选择性和对映选择性。DFT 计算表明亚胺离子中间体的 s-反式构象异构体比 s-顺式构象异构体更稳定。此外，计算出溴硝基甲烷阴离子对亚胺离子中间体的亲核攻击优先发生在吡咯烷亚胺中间体的大取代基的相反侧。

  DOI：

  10.1002/ejoc.201500838

文献信息

• Stereoselective Synthesis of Novel Types of Cyclopropyl Carbocyclic Nucleosides Containing Quaternary Stereogenic Centers
  作者：Elena Muray、Joan Rifé,、Vicenç Branchadell、Rosa M. Ortuño

  DOI：10.1021/jo025599v

  日期：2002.6.1

  of cyclopropyl carbocyclic nucleosides are described. The target products have been synthesized from suitable cyclopropane precursors obtained, in turn, from olefinic compounds derived from D-glyceraldehyde as a chiral precursor. Selective manipulation of the functional groups has allowed the preparation of enantiopure nucleosides, some of them displaying opposite chirality. All these molecules contain

  描述了新型的环丙基碳环核苷的多功能和立体控制合成词条。已经从合适的环丙烷前体合成了目标产物，所述合适的环丙烷前体又从作为手性前体的D-甘油醛衍生的烯烃化合物获得。官能团的选择性操作允许制备对映体纯的核苷，其中一些显示相反的手性。所有这些分子在环丙烷环的C-1或C-3处含有一个立体立体碳，并带有一个氨基，羟甲基或甲基作为附加取代基。在一种情况下，胸腺嘧啶直接与环丙烷连接。亚甲基单元用作其他合成核苷中的间隔基。
• 1,3-Dipolar Cycloadditions of Diazomethane to Chiral Electron-Deficient Olefins:  The Origin of the π-Facial Diastereoselection
  作者：Elena Muray、Angel Alvarez-Larena、Joan F. Piniella、Vicenç Branchadell、Rosa M. Ortuño

  DOI：10.1021/jo991227j

  日期：2000.1.1

  The stereochemical outcome of diazomethane cycloadditions to several chiral electron-deficient olefins has been investigated in order to establish the origin of the pi-facial diastereoselection. Nitro olefins, vinyl sulfones, enoates, and 2-amino enoates have been used for such a purpose. These substrates have been prepared from D-glyceraldehyde acetonide through Wittig-type condensations and present

  研究了重氮甲烷环加成到几种手性电子缺陷烯烃上的立体化学结果，以便确定pi非对映选择性的起源。硝基烯烃，乙烯基砜，烯酸酯和2-氨基烯酸酯已用于此目的。这些底物是由D-甘油醛丙酮化物通过Wittig型缩合反应制得的，并具有一个由庞大的二氧戊环提供的烷氧基取代基，该取代基与立体异构的烯丙基碳相连。在所有情况下，均已获得作为主要异构体的加合物，而与双键的Z / E立体化学以及取代基的数量和性质无关，不对称烯丙基碳的手性是造成非对映异构的唯一原因。
• Enantioselective synthetic approaches to cyclopropane and cyclobutane β-amino acids: synthesis and structural study of a conformationally constrained β-dipeptide
  作者：Marta Martı́n-Vilà、Elena Muray、Gemma P Aguado、Angel Alvarez-Larena、Vicenç Branchadell、Cristina Minguillón、Ernest Giralt、Rosa M Ortuño

  DOI：10.1016/s0957-4166(00)00297-4

  日期：2000.9

  Synthetic approaches to carbocyclic compounds, namely cyclopropane and cyclobutane beta -amino acids, are presented. One of them is based on enzymatic desymmetrization of meso diesters, leading to the enantioselective production of cis-hemiesters, which afforded beta -amino acids through Curtius rearrangements. The enantiomeric excess for the cyclobutane derivatives was 91% whereas the cyclopropanes were obtained in 63% ee. According to another strategy, an enantiomerically pure cyclopropane trans-beta -amino acid, bearing a quaternary center, has been synthesized from a homochiral precursor easily available from D-glyceraldehyde. The preparation and structural investigation of the first synthesized cyclobutane containing dipeptide is also described. A hairpin-like conformation of this molecule in the solid state has been demonstrated by X-ray structural analysis, showing crystal packing induced by the presence of the rigid cyclobutane moiety and the formation of intermolecular hydrogen bonds. NMR experiments confirmed that these molecules also tend to produce aggregates in solution. On the contrary, theoretical calculations suggest that intramolecular interactions are important in the gas phase, as expected. (C) 2000 Elsevier Science Ltd. All rights reserved.
• Asymmetric Nitrocyclopropanation of α-Substituted α,β-Enals Catalyzed by Diphenylprolinol Silyl Ether for the Construction of All-Carbon Quaternary ­Stereogenic Centers
  作者：Yujiro Hayashi、Tatsuya Yamazaki、Yuki Nakanishi、Tsuyoshi Ono、Tohru Taniguchi、Kenji Monde、Tadafumi Uchimaru

  DOI：10.1002/ejoc.201500838

  日期：2015.9

  The diphenylprolinol silyl ether mediated asymmetric nitrocyclopropanation of α-substituted α,β-unsaturated aldehydes with bromonitromethane, followed by base-promoted isomerization was found to afford trans-nitrocyclopropanecarbaldehydes with all-carbon quaternary stereogenic centers with excellent diastereo- and enantioselectivities. DFT calculations indicated that the s-trans conformer of the iminium

  发现二苯基脯氨醇甲硅烷基醚介导的 α-取代的 α,β-不饱和醛与溴硝基甲烷的不对称硝基环丙烷化，然后是碱促进的异构化，可提供具有全碳四元立体中心的反式硝基环丙烷甲醛，具有优异的非对映选择性和对映选择性。DFT 计算表明亚胺离子中间体的 s-反式构象异构体比 s-顺式构象异构体更稳定。此外，计算出溴硝基甲烷阴离子对亚胺离子中间体的亲核攻击优先发生在吡咯烷亚胺中间体的大取代基的相反侧。