(4R,5R)-2,2-Dimethyl-5-tetradecyl-[1,3]dioxolane-4-carbaldehyde | 1027896-10-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (4R,5R)-2,2-Dimethyl-5-tetradecyl-[1,3]dioxolane-4-carbaldehyde
• 英文别名: (4R,5R)-2,2-dimethyl-5-tetradecyl-1,3-dioxolane-4-carbaldehyde
• CAS: 1027896-10-1
• 化学式: C₂₀H₃₈O₃
• 分子量: 326.52
• InChiKey: QIVCWEQHFYQQLH-MOPGFXCFSA-N

物化性质

• 沸点：
  404.9±30.0 °C(predicted)
• 密度：
  0.929±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  7.3
• 重原子数：
  23
• 可旋转键数：
  14
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.95
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (4R,5R)-2,2-Dimethyl-5-tetradecyl-[1,3]dioxolane-4-carbaldehyde 在 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) 、 盐酸 、 4-二甲氨基吡啶 、 偶氮二异丁腈 、 palladium 10% on activated carbon 、 potassium tert-butylate 、 水 、 三正丁基氢锡 、 sodium hydride 、 二异丁基氢化铝 、 碳酸氢钠 、 对甲苯磺酸 、 乙酰氯 、 2,3-二氯-5,6-二氰基-1,4-苯醌 、 potassium hydroxide 、 环己烯 作用下， 以 四氢呋喃 、 甲醇 、 乙醇 、 正己烷 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 、 mineral oil 、 苯 为溶剂， 反应 108.17h， 生成 CRONY 101
  参考文献：
  名称：

  Intramolecular Nitrogen Delivery for the Synthesis of C-Glycosphingolipids. Application to the C-Glycoside of the Immunostimulant KRN7000

  摘要：

  The key reaction in this approach to C-glycosphingolipids is the stereoselective iodocyclization of a sugar-linked homoallylic carbonimidothioate. E and Z reaction substrates were assembled in a convergent fashion via an alkene metathesis strategy and exhibited the same alkene facial selectivity in the iodocyclization irrespective of alkene geometry, although the E alkene was found to be less reactive.

  DOI：

  10.1021/ol5002686
• 作为产物：
  描述：

  1-十四烯 在 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) 、 N-氯代丁二酰亚胺 、 2,2,6,6-四甲基哌啶氧化物 、 乙烯 、 palladium 10% on activated carbon 、 四丁基氯化铵 、 氢气 、 碳酸氢钠 、 potassium carbonate 作用下， 以 二氯甲烷 、 水 、 乙酸乙酯 为溶剂， 反应 30.0h， 生成 (4R,5R)-2,2-Dimethyl-5-tetradecyl-[1,3]dioxolane-4-carbaldehyde
  参考文献：
  名称：

  Intramolecular Nitrogen Delivery for the Synthesis of C-Glycosphingolipids. Application to the C-Glycoside of the Immunostimulant KRN7000

  摘要：

  The key reaction in this approach to C-glycosphingolipids is the stereoselective iodocyclization of a sugar-linked homoallylic carbonimidothioate. E and Z reaction substrates were assembled in a convergent fashion via an alkene metathesis strategy and exhibited the same alkene facial selectivity in the iodocyclization irrespective of alkene geometry, although the E alkene was found to be less reactive.

  DOI：

  10.1021/ol5002686

文献信息

• Preparation of <i>anti</i>-Vicinal Amino Alcohols: Asymmetric Synthesis of <scp>d</scp>-<i>erythro</i>-Sphinganine, (+)-Spisulosine, and <scp>d</scp>-<i>ribo</i>-Phytosphingosine
  作者：Ewen D. D. Calder、Ahmed M. Zaed、Andrew Sutherland

  DOI：10.1021/jo401211j

  日期：2013.7.19

  Overman rearrangement have been developed for the highly selective synthesis of anti-vicinal amino alcohol natural products. A MOM ether-directed palladium(II)-catalyzed rearrangement of an allylic trichloroacetimidate was used as the key step for the preparation of the protein kinase C inhibitor d-erythro-sphinganine and the antitumor agent (+)-spisulosine, whereas the Overman rearrangement of chiral

  已经开发了 Overman 重排的两种变体，用于抗连位氨基醇天然产物的高选择性合成。MOM 醚导向钯 (II) 催化的烯丙基三氯乙酰亚胺重排被用作制备蛋白激酶 C 抑制剂d-赤型-二氢鞘氨醇和抗肿瘤剂 (+)-spisulosine的关键步骤，而 Overman 重排手性烯丙基trichloroacetimidates通过不对称还原的α产生，β不饱和甲基酮允许快速访问既d -核糖-phytosphingosine和升-阿拉伯-phytosphingosine。
• Total synthesis of (2S,3S,4R)-2-[(2′R)-2-benzoyloxydocosanoylamino]-16-methylheptadecane-1,3,4,-triol 3,4-dibenzoate, a partially protected ceramide part of sponge cerebrosides
  作者：Hideki Nakashima、Norihiko Hirata、Takeru Iwamura、Yoshiro Yamagiwa、Tadao Kamikawa

  DOI：10.1039/p19940002849

  日期：——

  eptadecane-1,3,4-triol 3,4-dibenzoate 32, a partially protected ceramide part of a cerebroside from the marine sponge Halichondria japonica, has been synthesized from L-ascorbic acid, and its absolute stereochemistry has been determined. The key steps in the synthesis include the regioselective ring opening of chiral epoxide 5 with a 2-alkyl-2-lithio-1,3-dithiane and the introduction of a hydroxymethylene

  （2小号，3小号，4 - [R）-2 - [（2' - [R）-2- Benzoyloxydocosanoylamino] -16-methylheptadecane -1,3,4-三醇-3,4-二苯甲酸酯32，一个的部分保护的神经酰胺部分从海洋海绵哈立克氏菌中提取的脑苷脂是由L-抗坏血酸合成的，其绝对立体化学已经确定。合成的关键步骤包括用2-烷基-2-硫代-1,3-二硫杂环丁烷手性环氧化物5的区域选择性开环，并使用Dondoni的方法引入羟甲基合成子以组装C（1）和C（2 ）功能。
• Enantioselective Syntheses of<i>xylo</i>-C₁₈-Phytosphingosines using Double Stereodifferentiation
  作者：Pradeep Kumar、Rodney A. Fernandes

  DOI：10.1055/s-2003-36261

  日期：——

  The concept of double stereodifferentiation in Sharpless asymmetric dihydroxylation has been studied and the results obtained are applied to the diastereoselective syntheses of xylo-isomers of C18-phytosphingosine. The diastereomeric mixture obtained could be separated by column chromatography. Thus, the l-xylo-(2R,3S,4S)-C18- and d-xylo-(2S,3R,4R)-C18-phytosphing­osines as their tetraacetate derivatives were synthesized in dia­stereomerically pure form.

  研究了 Sharpless 不对称二羟基化过程中的双立体异构概念，并将所得结果应用于非对映选择性合成 C18-phytosphingosine 的 xylo 异构体。所获得的非对映异构体混合物可通过柱层析法进行分离。因此，以非对映纯形式合成了 l-xylo-(2R,3S,4S)-C18- 和 d-xylo-(2S,3R,4R)-C18-phytosphingosine 作为它们的四乙酸酯衍生物。
• Intramolecular Nitrogen Delivery for the Synthesis of C-Glycosphingolipids. Application to the C-Glycoside of the Immunostimulant KRN7000
  作者：Ahmad S. Altiti、David R. Mootoo

  DOI：10.1021/ol5002686

  日期：2014.3.7

  The key reaction in this approach to C-glycosphingolipids is the stereoselective iodocyclization of a sugar-linked homoallylic carbonimidothioate. E and Z reaction substrates were assembled in a convergent fashion via an alkene metathesis strategy and exhibited the same alkene facial selectivity in the iodocyclization irrespective of alkene geometry, although the E alkene was found to be less reactive.