(4S)-1,1-Dimethylethyl 4-(3'-methoxy-3'-oxo-1'-propenyl)-2,2-dimethyl-3-oxazolidinecarboxylate | 353520-76-0

• 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: (4S)-1,1-Dimethylethyl 4-(3'-methoxy-3'-oxo-1'-propenyl)-2,2-dimethyl-3-oxazolidinecarboxylate
• 英文别名: methyl 3-[(4'S)-N-tert-butoxycarbonyl-2',2'-dimethyloxazolidin-4'-yl]propenoate；tert-butyl (4S)-4-(3-methoxy-3-oxoprop-1-enyl)-2,2-dimethyl-1,3-oxazolidine-3-carboxylate
• CAS: 353520-76-0
• 化学式: C₁₄H₂₃NO₅
• 分子量: 285.34
• InChiKey: YSNYRLFAMVTFTM-JTQLQIEISA-N

物化性质

• 沸点：
  368.4±42.0 °C(Predicted)
• 密度：
  1.130±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  20
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  65.1
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (4S)-1,1-Dimethylethyl 4-(3'-methoxy-3'-oxo-1'-propenyl)-2,2-dimethyl-3-oxazolidinecarboxylate 在 盐酸 、 重铬酸吡啶 、 三甲基氯硅烷 、 potassium carbonate 、 对甲苯磺酸 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 10.0h， 生成 (2S,3R)-2-Amino-3-benzyl-1,5-pentanedioic acid hydrochloride
  参考文献：
  名称：

  Stereoselective synthesis of 3-alkylated glutamic acids: application to the synthesis of secokainic acid

  摘要：

  DOI：

  10.1021/jo00019a055
• 作为产物：
  描述：

  (R)-(+)-3-Boc-2,2-二甲基恶唑啉-4-甲醛 、 甲氧羰基亚甲基三苯基正膦 以 苯 为溶剂， 反应 12.0h， 以86%的产率得到(4S)-1,1-Dimethylethyl 4-(3'-methoxy-3'-oxo-1'-propenyl)-2,2-dimethyl-3-oxazolidinecarboxylate
  参考文献：
  名称：

  Effect of Alteration of the Heterocyclic Nucleus of Indolactam V on Its Isoform Selectivity for PKC. Palladium-Catalyzed Route to Benzofuran Analogs of ILV

  摘要：

  The discovery of isoform-selective modulators of protein kinase C (PKC) appears worthwhile in further defining the roles of the individual PKC isoforms in cell type-specific processes. In comparison with the phorbol esters, little information is available regarding the isoform selectivity of the teleocidin family. Blumberg has reported recently that 7-n-octylindolactam V exhibits little if any selectivity for the isoforms tested. In order to probe the possibility of developing isotype-selective agents based on the indolactam V (ILV) structure, we sought to explore replacement of the indole nucleus by a benzofuran ring. Herein we describe a novel palladium-catalyzed route to four benzofuran analogues 11a-d of ILV together with details of their isoform selectivity. Of considerable interest is the unexpected finding that this subtle N to O structural change leads to a compound (11b) that is modestly more like 12,13-dibutyrate phorbol and less like n-octyl-ILV in its pattern of activity. Moreover, the effect of introducing an additional stereocenter at C-14 into these benzofurans was explored, and a clear preference for R-stereochemistry at the C-14 center of the teleocidin family was found, thus providing additional verification of previously published structural correlations between the families of PKC activators. Overall, the present findings provide an important new direction in the quest for isoform-selective activators of PKC.

  DOI：

  10.1021/ja00130a003

文献信息

• Rhodium-Catalyzed Cyclohydrocarbonylation Approach to the Syntheses of Enantiopure Homokainoids
  作者：Wen-Hua Chiou、Angèle Schoenfelder、Liang Sun、André Mann、Iwao Ojima

  DOI：10.1021/jo070942n

  日期：2007.12.1

  homokainoids in an enantiomerically pure form were synthesized from enantiopure (R)- and (S)-Garner's aldehyde, featuring (i) the highly diastereoselective addition of alkenylcuprates to the acrylate intermediates and (ii) the Rh-catalyzed cyclohydrocarbonylation of homoallylic amine intermediates to construct the functionalized piperidine moiety in the key steps. For the introduction of a substituent at the 4-

  海藻酸的同系物是一种天然存在的强效谷氨酸受体激动剂，它是基于硬化的胡椒基谷氨酸结构设计的，由于其在中枢神经系统中的潜在活性，因此可以被视为同型类胡萝卜素。这些对映体纯净形式的新类化合物均由对映体（R）和（S）合成。）-加纳醛，其特征是（i）在丙烯酸酯中间体上高度非对映选择性地加成烯基铜酸酯，以及（ii）在关键步骤中Rh催化均烯丙基胺中间体的环氢羰基化反应以构建官能化的哌啶部分。为了在胡椒基谷氨酸的4位或5位引入取代基，使用了几种不同的策略，这些策略成功地导致了对映纯同型类化合物的形成。
• 1,2-Stereochemical Induction in the Pd^II-Catalyzed Conjugate Addition of Boronic Acids
  作者：Silvia Roscales、Francisco Sánchez、Aurelio G. Csákÿ

  DOI：10.1002/ejoc.201403488

  日期：2015.3

  2-chiral induction of the conjugate addition of boronic acids to enantiopure α,β-unsaturated ketones and esters without competition from the Mirozoki–Heck reaction. Bedford's palladacycle was found to control the stereoselectivity without the need for additional chiral ligands. We report that the PdII-catalyzed conjugate addition reaction between boronic acids and acyclic ketones or esters that bear a hydroxyl

  钯 (II) 催化已用于底物控制的 1,2-手性诱导硼酸与对映体纯 α,β-不饱和酮和酯的共轭加成反应，而不受 Mirozoki-Heck 反应的竞争。发现贝德福德的钯环无需额外的手性配体即可控制立体选择性。我们报告说，硼酸和在其 γ 位带有羟基取代基的无环酮或酯（甘油醛衍生物）之间的 PdII 催化的共轭加成反应可以提供高水平的抗立体选择，与之前报道的使用更昂贵的 RhI 催化剂相比. 另一方面，使用在其 γ 位带有氨基取代基的无环酯（丝氨酸衍生物）观察到高水平的顺式立体选择性。在这种情况下，