diethyl 2-[(4S)-4-(1-methylethyl)-2-oxo-3-oxazolidinyl]-2-oxoethanephosphonate | 147122-00-7

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机膦酸及其衍生物
• 英文名称: diethyl 2-[(4S)-4-(1-methylethyl)-2-oxo-3-oxazolidinyl]-2-oxoethanephosphonate
• 英文别名: (4S)-3-(2-diethoxyphosphorylacetyl)-4-propan-2-yl-1,3-oxazolidin-2-one
• CAS: 147122-00-7
• 化学式: C₁₂H₂₂NO₆P
• 分子量: 307.284
• InChiKey: RSFWQCKLUUQATP-SNVBAGLBSA-N

物化性质

• 沸点：
  437.1±28.0 °C(Predicted)
• 密度：
  1.211±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  20
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  82.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  diethyl 2-[(4S)-4-(1-methylethyl)-2-oxo-3-oxazolidinyl]-2-oxoethanephosphonate 在 palladium on activated charcoal 氢气 、 N,N-二异丙基乙胺 、 lithium chloride 作用下， 以 乙酸乙酯 、 乙腈 为溶剂， 反应 64.0h， 生成 (4S,4'S,5'S,6'R)-3-<5'-<(tert-Butyldiphenylsilyl)oxy>-6',7'-O-isopropylidene-4'-methylheptanoyl>-4-isopropyl-1,3-oxazolidin-2-one
  参考文献：
  名称：

  Studies on the synthesis of kijanolide: synthesis of the 2-acyl spirotetronate and investigations concerning the coupling of the top and bottom half fragments

  摘要：

  Several studies directed toward the synthesis of kijanolide are described. First, a method for synthesis of the 2-acyl spiro tetronate substructure (15,52) via a Dieckmann cyclization protocol was developed. Second, a 10-step synthesis of 7,7-dibromo-2,4-dimethyl-5-[(tert-butyldiphenylsilyl)oxy]heptenal 35 was developed, making possible the synthesis of a range of kijanolide bottom half precursors via olefination (e.g., 35 + 23 --> 38) and cross-coupling reactions (e.g., 38 --> 19). This solves the problems encountered due to the introduction of the C(7)-hydroxyl group in our previous synthesis of the kijanolide bottom half 2.2a Third, a highly efficient procedure was developed for the coupling of kijanolide top half 8 and dioxinone 38 via an acyl ketene intermediate. This is the most efficient of several methods examined for acylating the hindered tertiary hydroxyl group of 8. Attempts to perform the IMDA reaction of 46, 47 or 9 (R = SiEt3) generated in situ from coupling of 8 and the acyl ketene (20) derived from 42 were thwarted by the unexpected tendency of beta-keto esters like 47 to fragment and decarboxylate via the acyl ketene intermediate at temperatures above 115-degrees-C. 2-Acyl tetronates 53 and 54 were prepared, but these systems decomposed upon attempted IMDA cyclization at temperatures approaching 190-degrees-C.

  DOI：

  10.1021/jo00060a036
• 作为产物：
  描述：

  (S)-4-异丙基-2-唑烷酮 在 正丁基锂 作用下， 反应 1.17h， 生成 diethyl 2-[(4S)-4-(1-methylethyl)-2-oxo-3-oxazolidinyl]-2-oxoethanephosphonate
  参考文献：
  名称：

  Enantioselective preparation of .beta.-alkyl-.gamma.-butyrolactones from functionalized ketene dithioacetals

  摘要：

  An efficient and general enantioselective synthesis of beta-alkyl-gamma-butyrolactones has been developed. The key step of this procedure is an oxazolidinone-directed alkylation of a lithiated ketene dithioacetal that proceeds with excellent regiochemical control and high diastereofacial selectivity. Reductive removal of the chiral auxiliary followed by acid-induced cyclization of the resultant hydroxy ketene dithioacetal gives the enantiomerically pure beta-alkyl-gamma-butyrolactone.

  DOI：

  10.1021/jo00062a013

文献信息

• Stereoselective Synthesis of a Model C(18)–C(35) Spiroketal Fragment of Integramycin
  作者：Huikai Sun、Jason R. Abbott、William R. Roush

  DOI：10.1021/ol200834p

  日期：2011.5.20

  A highly stereoselective synthesis of a model C(18)–C(35) spiroketal unit (7) of integramycin has been accomplished via an enantioselective stannyl-crotylboration reaction and an N-iodosuccinimide-mediated spiroketalization of 19a.

  整合霉素的模型 C(18)–C(35) 螺缩酮单元 ( 7 ) 的高度立体选择性合成已通过对映选择性甲锡烷基-巴豆基硼酸化反应和N-碘代琥珀酰亚胺介导的19a螺缩酮化反应完成。
• Furans as Versatile Synthons: Total Syntheses of Caribenol A and Caribenol B
  作者：Hong-Dong Hao、Dirk Trauner

  DOI：10.1021/jacs.7b00234

  日期：2017.3.22

  caribenols A and B, were accessed from a common building block. Our synthesis of caribenol A features the diastereoselective formation of the seven-membered ring through a Friedel-Crafts triflation and a late-stage oxidation of a furan ring. The first synthesis of caribenol B was achieved using an intramolecular organocatalytic α-arylation. An unusual intramolecular aldol addition was developed for the

  两种复杂的norditerpenoids，caribenols A和B，是从一个共同的构建块获得的。我们合成 caribenol A 的特点是通过 Friedel-Crafts 三氟甲磺酸反应和呋喃环的后期氧化非对映选择性地形成七元环。caribenol B 的首次合成是使用分子内有机催化 α-芳基化实现的。一种不寻常的分子内醛醇加成被开发用于组装其环戊烯酮部分，而具有挑战性的反式二醇部分是通过选择性亲核加成到羟基 1,2-二酮来安装的。我们的整体合成策略也导致了两性内酯的第二代合成，证实了呋喃作为强大的亲核试剂和多功能合成子的有用性。
• Enantioselective preparation of .beta.-alkyl-.gamma.-butyrolactones from functionalized ketene dithioacetals
  作者：Stacie S. Canan Koch、A. Richard Chamberlin

  DOI：10.1021/jo00062a013

  日期：1993.5

  An efficient and general enantioselective synthesis of beta-alkyl-gamma-butyrolactones has been developed. The key step of this procedure is an oxazolidinone-directed alkylation of a lithiated ketene dithioacetal that proceeds with excellent regiochemical control and high diastereofacial selectivity. Reductive removal of the chiral auxiliary followed by acid-induced cyclization of the resultant hydroxy ketene dithioacetal gives the enantiomerically pure beta-alkyl-gamma-butyrolactone.
• A Formal Total Synthesis of (+)-Tetronolide, the Aglycon of the Tetrocarcins:  Enantio- and Diastereoselective Syntheses of the Octahydronaphthalene (Bottom-Half) and Spirotetronate (Top-Half) Fragments
  作者：William R. Roush、Melissa L. Reilly、Kazuo Koyama、Bradley B. Brown

  DOI：10.1021/jo970960c

  日期：1997.12.1

  A formal total synthesis of (+)-tetronolide, the aglycon of the tetrocarcins, has been achieved by virtue of the development of highly diastereo-and enantioselective syntheses of the bottom- and top-half fragments 4 and 5 reported herein. These fragments previously served as key intermediates in Yoshii's pioneering total synthesis of (+)-tetronolide, The synthesis of the bottom-half octahydronaphthalene unit 4 features the intramolecular Diels-Alder reaction of tetraenal 20 and proceeds in 17 steps and 5-6% yield from D-glyceraldehyde pentylidene acetal 8. The synthesis of the spirotetronate fragment 5 features the highly enantioselective exo selective Diels-Alder reaction of triene 37 and chiral dienophile 25b and proceeds in 14 steps and 10% overall yield from cis-2-butene-1,4-diol (38). An enantioselective synthesis of Boeckman's top-half cyclohexene fragment 6 sia the exo selective Diels-Alder reaction of diene 24 and dienophile 25a was also developed, but this route was deemed too inefficient for use in a projected total synthesis of the natural product. The syntheses of 5 and 6 provide important information on the utility of chiral dienophiles 25a and 25b in organic synthesis.
• Koch Stacie S. Canan, Chamberlin A. Richard, J. Org. Chem., 58 (1993) N 10, S 2725-2737
  作者：Koch Stacie S. Canan, Chamberlin A. Richard

  DOI：——

  日期：——