1-O-t-butyldiphenylsilyl-3,4-O-isopropylidene-L-erythrulose | 147107-70-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-O-t-butyldiphenylsilyl-3,4-O-isopropylidene-L-erythrulose
• 英文别名: 2-[tert-butyl(diphenyl)silyl]oxy-1-[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]ethanone
• CAS: 147107-70-8
• 化学式: C₂₃H₃₀O₄Si
• 分子量: 398.574
• InChiKey: GELHPEGSKJJQQP-NRFANRHFSA-N

物化性质

• 沸点：
  447.5±45.0 °C(Predicted)
• 密度：
  1.09±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.28
• 重原子数：
  28
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1-O-t-butyldiphenylsilyl-3,4-O-isopropylidene-L-erythrulose 在 Grubbs catalyst first generation 4-二甲氨基吡啶 、 copper(l) iodide 、 四丁基氟化铵 、 potassium hydride 、 三乙胺 、 magnesium bromide 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 生成 (2R,4'S)-2-(2,2-dimethyl-1,3-dioxolan-4-yl)-5-methyl-2-nonyl-3,6-dihydro-2H-pyran
  参考文献：
  名称：

  通过闭环烯烃复分解的立体选择性合成（+）-麦芽寡糖

  摘要：

  描述了由1-赤藓糖非常短和立体选择性地合成麦芽糖内酯的非天然对映体。合成的关键特征是聚氧酮的Felkin-Anh非对映选择性烯丙基化和我们小组最近描述的烯丙基化/复分解/烯丙基氧化方案。

  DOI：

  10.1016/s0040-4039(00)00884-4
• 作为产物：
  描述：

  ethyl (2R)-2-[(1S)-3,3-dimethyl(2,4-dioxolanyl)]-2-hydroxyacetate 在 咪唑 、 lithium aluminium tetrahydride 、 草酰氯 、 二甲基亚砜 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 33.5h， 生成 1-O-t-butyldiphenylsilyl-3,4-O-isopropylidene-L-erythrulose
  参考文献：
  名称：

  A Rapid Synthesis of Hexofuranose-like Iminosugars Using Ring-Closing Metathesis

  摘要：

  Two new 1-N-iminosugars have been prepared as hexofuranose analogues in an efficient manner by an RCM-based route. Both 3,4-disubstituted pyrrolidines display moderate inhibitory activity against Mycobacterium smegmatis galactan biosynthesis.

  DOI：

  10.1021/ol051232b

文献信息

• Synthetic study of cnicin: Synthesis of the side chain and its esterification
  作者：Manami Kurita、Miho Tanigawa、Shuhei Narita、Toyonobu Usuki

  DOI：10.1016/j.tetlet.2016.11.067

  日期：2016.12

  germacranolide sesquiterpene lactone that possesses potent inhibitory activity against the protozoan parasite Trypanosoma brucei, which causes human African trypanosomiasis (HAT). Although cnicin has an interesting structure and attractive biological activity, synthetic studies of cnicin have not yet been reported. This report describes the synthesis of the protected side chain carboxylic acid moiety at

  尼古丁是一种杀菌剂倍半萜内酯，对原虫寄生虫布鲁氏锥虫具有有效的抑制作用，布鲁氏锥虫引起人类非洲锥虫病（HAT）。尽管尼古丁具有令人感兴趣的结构和有吸引力的生物学活性，但尚未报道尼古丁的合成研究。本报告描述在cnicin的C8保护侧链的羧酸结构部分的合成通过从开始两条路线升抗坏血酸。此外，合成侧链和红红血lide内酯衍生物之间的酯化反应可以通过烟碱的水解和伯醇的保护来实现。因此，实现了尼古丁的半合成。
• Diastereoselectivity of the reactions of organolithium reagents with protected erythrulose oximes
  作者：J.A. Marco、M. Carda、J. Murga、S. Rodrı́guez、E. Falomir、M. Oliva

  DOI：10.1016/s0957-4166(98)00145-1

  日期：1998.5

  The addition of organolithium reagents to the CN bond of several erythrulose-derived chiral (E)- and (Z)-ketoxime ethers has been shown to be highly diastereoselective in the case of the (E)-isomers. Chelated and nonchelated transition states have been proposed to rationalize these results, with additional support of computational methods.

  有机锂试剂的几个赤藓酮糖衍生的手性（的CN键的加成ë） -和（Ž）-ketoxime醚已被证明是在（的情况下高度非对映ë） -异构体。已经提出了螯合和非螯合的过渡态来合理化这些结果，并附加了计算方法的支持。
• Diastereoselective additions of organolithium reagents to the CN bond of protected erythrulose oxime ethers. Synthesis of enantiopure α,α-disubstituted α-aminiacids
  作者：J.Alberto Marco、Miguel Carda、Juan Murga、Florenci González、Eva Falomir

  DOI：10.1016/s0040-4039(97)00165-2

  日期：1997.3

  The addition of organolithium reagents to the CN bond of several erythrulose-derived chiral (E)- and (Z)-ketoxime ethers has been shown to be highly diastereoselective for the (E)-isomers. A chelated transition state has been proposed to explain this result. The addition products were converted into the two α,α-disubstituted α-aminoacids (R)-2-(−)-methylserine and (R)-(+)-2-phenylserine.

  已经证明，将有机锂试剂加到几种由赤藻糖衍生的手性（E）-和（Z）-酮肟醚的CN键上对（E）-异构体具有很高的非对映选择性。已经提出了螯合的过渡态来解释该结果。将加成产物转化为两个α，α-二取代的α-氨基酸（R）-2-（-）-甲基丝氨酸和（R）-（+）-2-苯基丝氨酸。
• Synthesis of α,α-Disubstituted α-Amino Acid Derivatives in Enantiopure Form via Stereoselective Addition of Grignard Reagents to a Chiral Acyclic Nitrone Derived from L-Erythrulose
  作者：Raul Portolés、Juan Murga、Eva Falomir、Miguel Carda、Santiago Uriel、J. Alberto Marco

  DOI：10.1055/s-2002-25358

  日期：——

  The additions of various Grignard reagents to a chiral nitrone prepared from L-erythrulose take place with variable diastereoselectivity. The degree and strength of the facial selectivity can be modified if the reaction is performed in the presence of Lewis acidic additives: zinc bromide enhances attack to the si face whereas diethyl aluminum chloride promotes attack to the re side. The obtained adducts

  将各种格氏试剂添加到由 L-赤藓酮糖制备的手性硝酮中，具有可变的非对映选择性。如果反应在路易斯酸性添加剂的存在下进行，则可以改变表面选择性的程度和强度：溴化锌增强对硅表面的侵蚀，而二乙基氯化铝促进对背面的侵蚀。然后可以将获得的加合物有效地转化为受保护的 N-羟基 α,α-二取代 α-氨基酸衍生物以及相应的 α,α-二取代 α-氨基酸。
• Diastereoselectivity in Organometallic Additions to the Carbonyl Group of Protected Erythrulose Derivatives
  作者：J. Alberto Marco、Miguel Carda、Florenci González、Santiago Rodríguez、Encarna Castillo、Juan Murga

  DOI：10.1021/jo9716744

  日期：1998.2.1

  We have investigated a number of nucleophillic additions to L-erythrulose derivatives (4-12) bearing protective O-silyl, O-benzyl, and O-trityl groups in various relative positions. The results are discussed in the frame of chelated vs nonchelated transition states with additional support of previously published theoretical calculations. Sound evidence appears to exist for the formation of alpha-chelates as the key intermediates in nucleophillic additions to these alpha,beta-dioxygenated ketones. Since such evidence is still lacking in the case of beta-chelates, proposals of their intermediacy have been relegated in favor of the more solid Felkin-Anh model, which predicts the same stereochemical result. The behavior of these highly functionalized ketones does not always match that of structurally similar aldehydes.