(2S)-2-<(tert-butyldiphenylsilyl)oxy>-3-methylbutanal | 146861-20-3

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (2S)-2-<(tert-butyldiphenylsilyl)oxy>-3-methylbutanal
• 英文别名: (2S)-2-(tert-butyldiphenylsilyloxy)-3-methylbutanal；(S)-2-(tert-butyldiphenylsilyloxy)-3-methylbutanal；(2S)-2-[tert-butyl(diphenyl)silyl]oxy-3-methylbutanal
• CAS: 146861-20-3
• 化学式: C₂₁H₂₈O₂Si
• 分子量: 340.538
• InChiKey: GKBFJJNBWOFZJK-HXUWFJFHSA-N

物化性质

• 沸点：
  383.9±34.0 °C(Predicted)
• 密度：
  1.00±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.79
• 重原子数：
  24
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (2S)-2-<(tert-butyldiphenylsilyl)oxy>-3-methylbutanal 在 magnesium sulfate 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 26.0h， 生成 (3S,4S)-4-[(S)-1-(tert-Butyl-diphenyl-silanyloxy)-2-methyl-propyl]-3-methoxy-1-(4-methoxy-phenyl)-azetidin-2-one
  参考文献：
  名称：

  A new entry to 1,3-polyols, 2-amino 1,3-polyols, and .beta.-(1-hydroxyalkyl)isoserines using azetidinone frameworks as chiral templates via iterative asymmetric [2 + 2] cycloaddition reactions

  摘要：

  A new entry to polyfunctional compounds based on an iterative [2 + 2] asymmetric cycloaddition reaction of ketenes to O-protected alpha-hydroxy aldehyde derived imines is described for the first time.

  DOI：

  10.1021/jo00059a003
• 作为产物：
  描述：

  ethyl (2S)-2-hydroxy-3-methylbutanoate 在 咪唑 、 二异丁基氢化铝 作用下， 以 乙醚 、 正己烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 13.0h， 生成 (2S)-2-<(tert-butyldiphenylsilyl)oxy>-3-methylbutanal
  参考文献：
  名称：

  Enantioselective Total Synthesis of the Macrocyclic Spermidine Alkaloid (−)-Oncinotine

  摘要：

  The macrocyclic spermidine alkaloid (-)-oncinotine (1), isolated from Oncinotis nitida (Apocynaceae), was synthesized enantioselectively for the first time based on intramolecular iminium ion cyclization utilizing enantiomerically pure (2S)-N-[(benzyloxy)carbonyl]-2-piperidineacetaldehyde (8) as a chiral starting material. The required 8 was derived from the erythro adduct 16, which was obtained by diastereoselective 1,3-dipolar cycloaddition between 2,3,4,5-tetrahydropyridine 1-oxide (4) and (3S)-3-[(tert-butyldiphenylsilyl)oxy]-4-methyl-1-pentene (15). Wittig condensation of 8 with [8-(methoxycarbonyl)octyl]triphenylphosphonium iodide (21) followed by saponification provided the chiral piperidine moiety 23, which was coupled with the N-propyl-1,4-butanediamine segment 29 by using diethoxyphosphoryl cyanide in the presence of triethylamine to afford the tertiary amide 30. Conversion of 30 to the aldehyde 34 via desilylation and Swern oxidation, followed by hydrogenation over a palladium hydroxide catalyst under high dilution led to in situ formation of the transient iminium ion 35, which was further hydrogenated to form 33 in a single operation. Subsequent removal of the Boc protecting group resulted in (-)-oncinotine (1).

  DOI：

  10.1021/jo9518258

文献信息

• Rhodium-Catalyzed Methylenation of Aldehydes
  作者：Hélène Lebel、Valérie Paquet

  DOI：10.1021/ja038112o

  日期：2004.1.1

  The rhodium-catalyzed methylenation of aldehydes using trimethylsilyldiazomethane and triphenylphosphine produces a variety of terminal alkenes in excellent yields. These mild and nonbasic reaction conditions allow the conversion of enolizable substrates (keto aldehydes and nonracemic alpha-substituted aldehydes) to terminal alkenes without epimerization. Optimization of the reaction conditions led

  使用三甲基甲硅烷基重氮甲烷和三苯基膦对醛进行铑催化的亚甲基化反应，以优异的收率生成多种末端烯烃。这些温和且非碱性的反应条件允许可烯醇化的底物（酮醛和非外消旋 α 取代醛）转化为末端烯烃，而无需差向异构化。反应条件的优化得出的结论是，多种铑 (I) 源可用作催化剂。还研究了溶剂对反应的影响，表明虽然四氢呋喃是最好的溶剂，但也可以使用其他溶剂。系统的反应性很大程度上取决于膦试剂的性质。还描述了易于去除的膦的使用。
• Synthesis of Enantiopure Substituted Piperidines <i>via</i> an Aziridinium Ring Expansion
  作者：Scott B. D. Jarvis、Andre B. Charette

  DOI：10.1021/ol201349k

  日期：2011.8.5

  piperidines from readily available chiral building blocks. This method, which features a novel irreversible dihydropyrole-tetrahydropyridine ring expansion, allows the introduction of a large variety of substituents at the 3-position and permits substitution at the 2- and 6-position giving mono-, di-, or trisubstituted piperidines with high diastereocontrol.

  在这里，我们报道了一种新的方法，用于从容易获得的手性结构单元中不对称合成3取代的哌啶。该方法具有新颖的不可逆的二氢吡咯-四氢吡啶环扩环的特征，它允许在3位引入多种取代基，并允许在2位和6位取代，从而得到单，二或三取代的哌啶高非对映控制。
• Reaction of chiral titanium Z-enolates with chiral α-silyloxy aldehydes. Syntheses of NFX-2 and Antimycinone
  作者：Cristina Esteve、Mònica Ferreró、Pedro Romea、Fèlix Urpí、Jaume Vilarrasa

  DOI：10.1016/s0040-4039(99)00987-9

  日期：1999.7

  Titanium-mediated aldol reactions of 1 and (S)-2-tert-butyldiphenylsilyloxy aldehydes (matched pair) afford syn Felkin diastereomers in excellent yield and absolute stereochemical control. Having established that chain length does not affect the yield of the titanium aldol reactions we have been able to achieve short, high yielding and enantioselective syntheses of NFX-2 and Antimycinone.

  钛介导的1和（S）-2-叔丁基二苯基甲硅烷氧基醛（匹配对）的醇醛缩合反应可提供出色的收率和绝对的立体化学控制的合成Felkin非对映异构体。确定链长不会影响钛醇醛缩合反应的收率，我们已经能够实现NFX-2和抗霉素的短，高收率和对映选择性合成。
• Reaction of achiral titanium Z-enolates with chiral α-silyloxy aldehydes
  作者：Cristina Esteve、Mònica Ferreró、Pedro Romea、Fèlix Urpí、Jaume Vilarrasa

  DOI：10.1016/s0040-4039(99)00986-7

  日期：1999.7

  Aldol reactions between the putative Z-enolate derived from 2-methyl-3-pentanone and several chiral alpha-tert-butyldiphenylsilyloxy aldehydes have been studied. The stereochemical outcome suggests that stereoelectronic effects play a dominant role in these reactions and the results can be accommodated by the Felkin model, with gauche pentane interactions being less important. (C) 1999 Elsevier Science Ltd. All rights reserved.
• A new entry to 1,3-polyols, 2-amino 1,3-polyols, and .beta.-(1-hydroxyalkyl)isoserines using azetidinone frameworks as chiral templates via iterative asymmetric [2 + 2] cycloaddition reactions
  作者：Claudio Palomo、Jesus M. Aizpurua、Raquel Urchegui、Jesus M. Garcia

  DOI：10.1021/jo00059a003

  日期：1993.3

  A new entry to polyfunctional compounds based on an iterative [2 + 2] asymmetric cycloaddition reaction of ketenes to O-protected alpha-hydroxy aldehyde derived imines is described for the first time.