(3R,4S,11R)-11-Acetoxy-1-diazo-3,4-epoxydodecan-2-one | 124887-08-7

• 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: (3R,4S,11R)-11-Acetoxy-1-diazo-3,4-epoxydodecan-2-one
• CAS: 124887-08-7
• 化学式: C₁₄H₂₂N₂O₄
• 分子量: 282.34
• InChiKey: OWEJBRMSQUWTFC-SWHYSGLUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.92
• 重原子数：
  20.0
• 可旋转键数：
  10.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  92.3
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  (3R,4S,11R)-11-Acetoxy-1-diazo-3,4-epoxydodecan-2-one 在 4-二甲氨基吡啶 咪唑 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 4.5h， 生成 Ethyl (2E,4S,11R)-11-acetoxy-4-(tert-butyldimethylsiloxy)-2-dodecenoate
  参考文献：
  名称：

  Total synthesis of patulolide C and its homo-, nor, and iso analogs

  摘要：

  The stereospecific total synthesis of the naturally occurring macrolide patulolide C 19Eb as well as its iso, nor, and homo analogs is described by applying the photoinduced rearrangement of enantiomerically pure epoxy diazomethyl ketones 14 to gamma-hydroxy alpha,beta-unsaturated esters 15 as the key step. The required epoxy diazomethyl ketones 14 are obtained by a Sharpless epoxidation of an appropriate allylic alcohol, followed by ruthenium tetraoxide oxidation to an oxiranecarboxylic acid, conversion into a mixed anhydride, and treatment with diazomethane. Macrolide 19Zb, which is a geometrical isomer of 19Eb, turned out to be a diastereomer of natural macrolide isopatulolide C, which implies the 4R,11R configuration for this natural material. X-ray diffraction analyses of 19Ea and 19Eb show that there is a considerable difference in spatial arrangement; particularly, the different torsion angles between the carbonyl and olefinic bonds are note worthy. The conformational behavior of these macrolides is also deduced from the NMR and UV spectra.

  DOI：

  10.1021/jo00077a047
• 作为产物：
  描述：

  (2R,3S)-3-[(7R)-7-acetyloxyoctyl]oxirane-2-carboxylic acid 在 三乙胺 作用下， 以 乙醚 为溶剂， 反应 1.0h， 生成 (3R,4S,11R)-11-Acetoxy-1-diazo-3,4-epoxydodecan-2-one
  参考文献：
  名称：

  Total synthesis of patulolide C and its homo-, nor, and iso analogs

  摘要：

  The stereospecific total synthesis of the naturally occurring macrolide patulolide C 19Eb as well as its iso, nor, and homo analogs is described by applying the photoinduced rearrangement of enantiomerically pure epoxy diazomethyl ketones 14 to gamma-hydroxy alpha,beta-unsaturated esters 15 as the key step. The required epoxy diazomethyl ketones 14 are obtained by a Sharpless epoxidation of an appropriate allylic alcohol, followed by ruthenium tetraoxide oxidation to an oxiranecarboxylic acid, conversion into a mixed anhydride, and treatment with diazomethane. Macrolide 19Zb, which is a geometrical isomer of 19Eb, turned out to be a diastereomer of natural macrolide isopatulolide C, which implies the 4R,11R configuration for this natural material. X-ray diffraction analyses of 19Ea and 19Eb show that there is a considerable difference in spatial arrangement; particularly, the different torsion angles between the carbonyl and olefinic bonds are note worthy. The conformational behavior of these macrolides is also deduced from the NMR and UV spectra.

  DOI：

  10.1021/jo00077a047

文献信息

• A general stereospecific synthesis of γ-hydroxy-α,β-unsaturated esters
  作者：L. Thijs、F.J. Dommerholt、F.M.C. Leemhuis、B. Zwanenburg

  DOI：10.1016/s0040-4039(00)97124-7

  日期：1990.1

  α,β-unsaturated esters is achieved, involving successively the Sharpless epoxidation of allylic alcohols, oxidation to glycidic acids, conversion into α,β-epoxy diazomethyl ketones, and irradiation in ethanol at 300 nm. Intermediates in the photo-induced rearrangement are epoxy ketenes, which undergo ethanolysis with simultaneous opening of the epoxide, preferably via a transition state involving the

  实现了旋光性γ-羟基.α，β-不饱和酯的立体定向合成，依次涉及烯丙醇的Sharpless环氧化，氧化为缩水甘油酸，转化为α，β-环氧重氮甲基酮和在300 nm的乙醇中辐照。在光诱导的重排中的中间体是环氧乙烯酮，其经历乙醇化并同时打开环氧化物，优选通过涉及s-反式构象的过渡态。
• An enantioselective total synthesis of the macrolide Patulolide C
  作者：L. Thijs、D.M. Egenberger、B. Zwanenburg

  DOI：10.1016/s0040-4039(01)93736-0

  日期：1989.1

  described. The essentials of this synthesis are: nucleophilic ring opening of R-methyloxirane with a lithium acetylide, a Sharpless epoxidation, strategic use of the photochemical rearrangement of an epoxy diazomethyl ketone to a γ-hydroxy-α,β-unsaturated ester and a macro-lactonization using 2,6-dichlorobenzoyl chloride.

  描述了十二元环内酯帕特洛立德C的全合成。这种合成的基本要素是：R-甲基环氧乙烷与乙炔锂的亲核开环，无尖锐的环氧化，将环氧重氮甲基酮进行光化学重排为γ-羟基-α，β-不饱和酯和大分子使用2，6-二氯苯甲酰氯进行内酯化。
• THIJS, L.;EGENBERGER, D. M.;ZWANENBURG, B., TETRAHEDRON LETT., 30,(1989) N6, C. 2153-2156
  作者：THIJS, L.、EGENBERGER, D. M.、ZWANENBURG, B.

  DOI：——

  日期：——
• THIJS, L.;DOMMERHOLT, F. J.;LEEMHUIS, F. M. C.;ZWANENBURG, B., TETRAHEDRON LETT., 31,(1990) N5, C. 6589-6592
  作者：THIJS, L.、DOMMERHOLT, F. J.、LEEMHUIS, F. M. C.、ZWANENBURG, B.

  DOI：——

  日期：——