(R)-4,4-dimethyl-2-oxotetrahydrofuran-3-yl 3-oxobutanoate | 186899-17-2

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 酮酸及其衍生物
• 英文名称: (R)-4,4-dimethyl-2-oxotetrahydrofuran-3-yl 3-oxobutanoate
• 英文别名: [(3R)-4,4-dimethyl-2-oxooxolan-3-yl] 3-oxobutanoate
• CAS: 186899-17-2
• 化学式: C₁₀H₁₄O₅
• 分子量: 214.218
• InChiKey: NWOWKNKNCYGBIE-QMMMGPOBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  69.7
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (R)-4,4-dimethyl-2-oxotetrahydrofuran-3-yl 3-oxobutanoate 在 4-乙酰氨基苯磺酰叠氮 、 三乙胺 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 30.0h， 生成 (R)-tetrahydro-4,4-dimethyl-2-oxo-3-furanyl 2-diazo-3-[(1,1-dimethylethyl)dimethylsiloxy]-3-butenoate
  参考文献：
  名称：

  高度官能化的 8-氧杂双环 [3.2.1] 辛烯衍生物的不对称合成

  摘要：

  在呋喃的存在下，羧酸铑 (II) 催化乙烯基重氮甲烷的分解导致一般合成氧杂双环 [3.2.1] octa-2,6-二烯衍生物。这些氧双环产品是有机合成中的通用中间体。[3 + 4] 环化的机制被认为是串联环丙烷化/Cope 重排。这种机制与在这些 [3 + 4] 环中观察到的出色的区域和立体控制是一致的。通过使用铑（II）（S）-N-（叔丁基苯）磺酰基脯氨酸盐作为催化剂或使用（S）-乳酸盐或（R）-泛内酯作为类卡宾的手性助剂，可以不对称合成氧杂双环产物。

  DOI：

  10.1021/ja962081y
• 作为产物：
  描述：

  双乙烯酮 、 D-(-)-泛酰内酯 生成 (R)-4,4-dimethyl-2-oxotetrahydrofuran-3-yl 3-oxobutanoate
  参考文献：
  名称：

  铑稳定的乙烯基类胡萝卜素与吡咯的反应，对映体的对映选择性合成

  摘要：

  在N-（叔丁氧基羰基）吡咯存在下，铑（II）催化含有（R）-泛内酯或（S）-乳酸酯作为手性助剂的乙烯基重氮甲烷的分解，导致串联环丙烷化/对映体重排对映烷烃进入对映烷。

  DOI：

  10.1016/s0040-4039(00)60899-7

文献信息

• Formal Synthesis of (−)-Englerin A and Cytotoxicity Studies of Truncated Englerins
  作者：Jing Xu、Eduardo J. E. Caro-Diaz、Ayse Batova、Steven D. E. Sullivan、Emmanuel A. Theodorakis

  DOI：10.1002/asia.201101021

  日期：2012.5

  An efficient formal synthesis of (−)‐englerin A (1) is reported. The target molecule is a recently isolated guaiane sesquiterpene that possesses highly potent and selective activity against renal cancer cell‐lines. Our enantioselective strategy involved the construction of the BC ring system of compound 1 through a RhII‐catalyzed [4+3] cycloaddition reaction followed by subsequent attachment of the

  报道了 (-)-englerin A ( 1 )的有效形式合成。目标分子是最近分离的愈创木酚倍半萜烯，它对肾癌细胞系具有高效和选择性的活性。我们的对映选择性策略涉及通过 Rh II构建化合物1的 BC 环系统-催化的 [4+3] 环加成反应，随后通过分子内醛醇缩合反应连接 A 环。因此，该策略允许合成截断的 englerins。用 A498 肾癌细胞系对这些类似物进行评估表明，englerin 的 A 环对其抗增殖活性至关重要。此外，对这些类似物的评估导致鉴定了 CEM 细胞的强效生长抑制剂，其 GI 50值在 1-3 μM范围内。
• Preparation of optically active α-silylcarbonyl compounds using asymmetric alkylation of α-silylacetic esters and asymmetric metal-carbene insertion into the SiH bond
  作者：Yannick Landais、Denis Planchenault

  DOI：10.1016/s0040-4020(97)00002-1

  日期：1997.2

  Substituted α-silylacetic esters have been prepared in good yields and with reasonable diastereoselectivities by three different routes. The first two involved alkylation of the parent α-silylacetic ester enolates, with the chiral auxiliaries being present either on silicon or on the ester function. The third route involving asymmetric insertion of metal-carbenoids into the SiH bond was found to afford

  已经通过三种不同的途径以高收率和合理的非对映选择性制备了取代的α-甲硅烷基酯。前两个涉及母体α-甲硅烷基酯烯酸酯的烷基化，其中手性助剂存在于硅或酯官能团上。使用泛内酯作为手性助剂，发现第三种途径涉及将金属类金属化合物不对称地插入SiH键中，从而提供更好的非对映选择性。
• Catalyzed addition of diazoacetoacetates to imines: synthesis of highly functionalized aziridines
  作者：Xue-jing Zhang、Ming Yan、Dan Huang

  DOI：10.1039/b813763c

  日期：——

  The addition of diazoacetoacetates to aromatic imines derived from p-methoxyaniline is achieved using dirhodium tetraacetate as the catalyst. Highly functionalized aziridines are obtained in good yield and with excellent stereoselectivity. 2-Diazo-1,3-diketones also provide good yields of aziridines, but dimethyl diazomalonate is inactive in the transformation. The diazoacetoacetates of chiral alcohols are also examined in the reaction and moderate diastereoselectivity is achieved with (R)-pantolactone-derived diazoacetoacetate. A reaction mechanism through metal-carbene and azomethine ylide is proposed.

  将二氮基乙酸酯添加到由对甲氧基苯胺衍生的芳香亚胺中，使用四乙酸二铑作为催化剂。可以获得高度功能化的氮杂环丙烯，产率良好且立体选择性优异。2-二氮基-1,3-二酮也能提供良好的氮杂环丙烯产率，但二甲基二氮基马来酸酯在此转化中无活性。还对手性醇的二氮基乙酸酯进行了反应研究，使用(R)-潘托乳酸衍生的二氮基乙酸酯实现了中等的非对映选择性。提出了一种通过金属-烯烃和亚胺亚氢化物的反应机制。
• Enantioselective Synthesis of Functionalized Tropanes by Rhodium(II) Carboxylate-Catalyzed Decomposition of Vinyldiazomethanes in the Presence of Pyrroles
  作者：Huw M. L. Davies、Julius J. Matasi、L. Mark Hodges、Nicholas J. S. Huby、Craig Thornley、Norman Kong、Jeffrey H. Houser

  DOI：10.1021/jo961920w

  日期：1997.2.1

  A series of enantiomerically enriched tropanes was synthesized by the rhodium(II) octanoate-catalyzed reaction of various N-BOC-protected pyrroles with vinyldiazomethanes. The overall 3 + 4 annulation occurs by a tandem cyclopropanation/Cope rearrangement. Asymmetric induction was best achieved in these transformations by using either (S)-lactate or (R)-pantolactone as a chiral auxiliary on the vinyldiazomethanes. Reactions carried out with the chiral catalyst tetrakis[N-( 4-tert-butylbenzenesulfonyl)-(L)-prolinato]dirhodium (2) provided moderate asymmetric induction, but also resulted in the formation of isomeric azabicyclooctane side products. The utility of the synthetic process was demonstrated through the asymmetric synthesis of(-)-anhydroecgonine methyl ester and (-)-ferruginine.
• α,α′-Dioxothiones part 2. Asymmetric Diels-Alder reactions of chiral non-racemic α,α′-dioxothiones
  作者：Giorgio Boccardo、Giuseppe Capozzi、Meri Giuntini、Stefano Menichetti、Cristina Nativi

  DOI：10.1016/s0040-4020(97)10162-4

  日期：1997.12

  Chiral non-racemic alpha,alpha'-dioxothiones 2a-g and 17 are obtained from chiral beta-ketoesters using the phthalimidesulfenyl chloride 1 as key reagent. The ability of these thiones to discriminate between the enantiotopic faces of several dienophiles has been evaluated, The best diastereoisomeric excesses (67-80%) were obtained when the alpha-acyl thiones were involved as electron-poor dienes in inverse electron demand Diels-Alder reactions with electron-rich styrenes as dienophiles. The possibility to obtain thiones bearing two,chiral groups as-well as the reactions where the alpha-acyl thiones 2 participate as dienophiles are also shown. (C) 1997 Elsevier Science Ltd.