(4R,6R)-4,6-bis(bromomethyl)-2,2-dimethyl-1,3-dioxane | 130275-04-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (4R,6R)-4,6-bis(bromomethyl)-2,2-dimethyl-1,3-dioxane
• CAS: 130275-04-6
• 化学式: C₈H₁₄Br₂O₂
• 分子量: 302.006
• InChiKey: WUKCHOVCTNKYPN-RNFRBKRXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (4R,6R)-4,6-bis(bromomethyl)-2,2-dimethyl-1,3-dioxane 在 lithium diethylamide 作用下， 生成 (2R,3S,5R,7R,9R,11R,13R,15S,16E,18R,19R)-7,13-di-cyano-19-O-((1,1-dimethylethyl)dimethylsilyl)-1,3:5,7:9,11:13,15-tetrakis-O-(methylethylidene)-2,18,20-trimethyl-16-heneicosene-1,3,5,7,9,11,13,15,19-momol
  参考文献：
  名称：

  Synthesis of the polyol chain of (-)-roxaticin.

  摘要：

  Tetraacetonide 19, which incorporates the 10 stereogenic centers of (-)-roxaticin, was chosen as a test case to develop a convergent synthesis of alternating polyol chains. This synthesis uses a stepwise alkylation of dibromide 16 followed by a stereoselective reductive decyanation in a three-fold convergent strategy.

  DOI：

  10.1021/jo00044a007
• 作为产物：
  描述：

  2,4-戊二酮,1,5-二氯 在 Ru2Cl4{2,2'-bis(diphenylphosphino)-1,1'-binaphthyl}2*N(C2H5)3 氢氧化钾 、 dilithium tetrabromonickelate(II) 、 camphor-10-sulfonic acid 、 氢气 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 丙酮 为溶剂， 25.0~102.0 ℃ 、8.62 MPa 条件下， 反应 22.0h， 生成 (4R,6R)-4,6-bis(bromomethyl)-2,2-dimethyl-1,3-dioxane
  参考文献：
  名称：

  Optically pure 1,3-diols from (2R,4R)- and (2S,4S)-1,2:4,5-diepoxypentane

  摘要：

  Optically pure (> 97% ee) (2R,4R)-1,2:4,5-diepoxypentane (1) and its enantiomer can be prepared in three steps from 2,4-pentanedione without the need for chromatographic purification. Diepoxide 1 is an efficient precursor to a wide variety of optically pure syn and anti 1,3-diols. Reaction with excess nucleophile gives symmetric[GRAPHICS]anti 1,3-diols in good yield. Reaction with a slight excess of alkyllithium under Ganem's conditions gives the monoepoxides 5 in good yield. Addition of a second nucleophile to monoepoxide 5 gives asymmetric anti 1,3-diols. Mitsunobu inversion of monoepoxide 5 followed by addition of a second nucleophile gives syn 1,3-diols. Optically pure syn and anti 1,3-diols are available from diepoxide 1 in one to three steps and good overall yield.

  DOI：

  10.1021/jo00017a032

文献信息

• Convergent Synthesis of the Polyene Macrolide (-)-Roxaticin
  作者：Scott D. Rychnovsky、Rebecca C. Hoye

  DOI：10.1021/ja00084a017

  日期：1994.3

  ether followed by elaboration of the polyene using Wollenberg's method gave a tetraenal. The macrocyclic ring was closed using an intramolecular Horner-Emmons Wittig reaction, and acid-catalyzed deprotection completed the synthesis of roxaticin. Our synthesis of roxaticin illustrates a first generation approach to the highly convergent synthesis of polyene macrolide antibiotics that should ultimately

  (-)-Roxaticin 是由多元醇四丙酮化物 5 合成的，它是通过三重收敛路线制备的。使用 Noyori 不对称氢化制备每个光学纯的结构单元（2、3 和 4）。二溴化物 3 与氰醇丙酮化物 2 和 4 连续烷基化，然后立体选择性还原脱氰得到四丙酮化物 5。 由于多烯链对氧化脱保护的不稳定性，最初在关键保护步骤中使用 1-甲基环丙基醚制备罗沙星的方法未成功。1,3-苯并二硫戊环-2-基 (BDT) 醚在模型研究中表现良好，并用于 roxaticin 系统。将 roxaticin 前体保护为 BDT 醚，然后使用 Wollenberg 方法制备多烯，得到四烯醛。大环使用分子内Horner-Emmons Wittig反应闭合，酸催化脱保护完成roxaticin的合成。我们合成 roxaticin 说明了多烯大环内酯类抗生素的高度收敛合成的第一代方法，最终可用于制备立体化学和结构类似物
• Stereochemical Determination of Roflamycoin: 13C Acetonide Analysis and Synthetic Correlation
  作者：Scott D. Rychnovsky、George Griesgraber、Rolf Schlegel

  DOI：10.1021/ja00106a024

  日期：1995.1

  The relative configuration of natural roflamycoin (1) was determined by C-13 acetonide analysis, combined with other supporting spectroscopic data. A previous proposal for the configuration of roflamycoin was shown to be incorrect. The absolute configuration was determined by the advanced Mosher's method. Our proposed structure of natural roflamycoin was confirmed by the synthesis of a degradation fragment that incorporates all of the 11 independent stereogenic centers of roflamycoin. The complete structure of roflamycoin is illustrated in Figure 1.
• Total Synthesis of the Polyene Macrolide Roflamycoin
  作者：Scott D. Rychnovsky、Uday R. Khire、Guang Yang

  DOI：10.1021/ja963800b

  日期：1997.2.1