2-(tert-butyldimethylsilyloxy)-2-cyclohexylacetaldehyde | 89869-03-4

• 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: 2-(tert-butyldimethylsilyloxy)-2-cyclohexylacetaldehyde
• 英文别名: (tert-butyldimethylsilyloxy)(cyclohexyl)acetaldehyde；2-[Tert-butyl(dimethyl)silyl]oxy-2-cyclohexylacetaldehyde
• CAS: 89869-03-4
• 化学式: C₁₄H₂₈O₂Si
• 分子量: 256.461
• InChiKey: SOHCRMFINHKLGE-UHFFFAOYSA-N

物化性质

• 沸点：
  283.1±23.0 °C(Predicted)
• 密度：
  0.914±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.16
• 重原子数：
  17
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.93
• 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：

  2-(tert-butyldimethylsilyloxy)-2-cyclohexylacetaldehyde 在 indium 、 对甲苯磺酸 作用下， 以 甲醇 、 水 为溶剂， 反应 32.0h， 生成 (4S,5R)-5-[(R)-cyclohexyl(hydroxy)methyl]-4-methyl-3-methylideneoxolan-2-one
  参考文献：
  名称：

  Experimental Test of Setting Three Contiguous Stereogenic Centers in Water. Diastereoselective Coupling of Geometrically Biased Allylic Bromides to α-Oxy Aldehydes with Indium

  摘要：

  Indium-promoted additions of (Z)-2-(bromomethyl)-2-butenoate to several alpha-(tert-butyldimethylsiloxy) and alpha-(benzyloxy) aldehydes in water have been examined in order to assess the direction and sense of asymmetric induction in these coupling reactions. High levels of the 3,4-syn;4,5-anti diastereomers were produced, reflecting the promising synthetic potential of this chemistry. This stereodifferentiation has been attributed to the strong geometric bias exercised by this allylindium reagent and adherence to a Felkin-Ahn transition-state alignment. Support for this interpretation was gained by comparing the fate of (E)-cinnamyl bromide under comparable circumstances. In this case, the 3,4-anti;4,5-anti diastereomer predominated as expected.

  DOI：

  10.1021/jo970267p
• 作为产物：
  描述：

  1-tert-butyldimethylsilyloxycyclohex-1-enyl-prop-2-ene 在 臭氧 、 三苯基膦 作用下， 以 二氯甲烷 为溶剂， 反应 6.0h， 以79%的产率得到2-(tert-butyldimethylsilyloxy)-2-cyclohexylacetaldehyde
  参考文献：
  名称：

  二异丁基氢化铝促进的醛的Tishchenko反应及其在大环内酯形成中的应用

  摘要：

  脂肪醛与正戊烷中催化量的Dibal-H反应，以良好至极好的收率得到相应的季申科产品。相反，在类似条件下，α-甲硅烷氧基醛通过Oppenauer氧化生成α-甲硅烷氧基酮。ω-烯烃醛的Tishchenko反应，然后进行RCM和氢化提供了一种方便的方法来制备11-37元大环内酯。

  DOI：

  10.1016/j.tet.2007.08.074

文献信息

• Practical hydroxymethylation of aldehydes and ketones via pinacol cross-coupling reactions with paraformaldehyde
  作者：Jeonghan Park、Steven F. Pedersen

  DOI：10.1016/s0040-4020(01)88875-x

  日期：——

  method for the direct hydroxymethylation of aldehydes and ketones via pinacol cross-coupling with paraformaldehyde is described. The reaction is promoted by vanadium(II) ions which are conveniently generated from the reduction of VCl3(THF)3 with zinc dust. Excellent yields of terminal diols are obtained and stereoselective coupling is observed with some chiral aldehydes and ketones.

  描述了通过频哪醇与多聚甲醛交叉偶联直接醛和酮进行羟甲基化的一般实用方法。钒（II）离子可促进反应，钒离子可通过用锌粉还原VCl 3（THF）3方便地产生。获得了优异的末端二醇收率，并且观察到与一些手性醛和酮的立体选择性偶联。
• Reduction of α-trialkylsiloxy nitriles with diisobutylaluminium hydride (DIBAH): A facile preparation of α-trialkylsiloxy aldehydes and their derivatives
  作者：Masahiko Hayashi、Tomoko Yoshiga、Kanako Nakatani、Kazuyuki Ono、Nobuki Oguni

  DOI：10.1016/s0040-4020(01)86995-7

  日期：1994.2

  could be achieved via the reduction of α-trimethylsiloxy nitriles with diisobutylaluminium hydride (DIBAH) starting from a variety of ketones. The facile synthesis of optically active α-tert-butyldimethylsiloxy aldehydes was attained by combination of asymmetric silylcyanation of aldehydes and DIBAH reduction of optically active α-siloxy nitriles. Furthermore, in the reduction of some α-tert-butyldimethylsiloxy-β

  α-三甲基甲硅烷氧基醛和α-羟基醛的逐步合成可以通过从多种酮开始用氢化二异丁基铝（DIBAH）还原α-三甲基甲硅烷氧基腈来实现。通过醛的不对称甲硅烷基氰化和光学活性α-甲硅烷氧基腈的DIBAH还原相结合，可以轻松合成光学活性的α-叔丁基二甲基甲硅烷氧基醛。此外，在某些反应条件下，在某些α-叔丁基二甲基甲硅烷氧基-β，γ-不饱和腈的还原中，发生了双键的迁移以形成更稳定的α-甲硅烷氧基-α，β-不饱和醛。
• Stereochemical aspects of the asymmetric synthesis of chiral α,β-dihydroxy phosphonates. Synthesis of α,β-dihydroxy phosphonic acids
  作者：Alessandro Bongini、Roberto Camerini、Mauro Panunzio、Elisa Bandini、Giorgio Martelli、Giuseppe Spunta

  DOI：10.1016/s0957-4166(96)00456-9

  日期：1996.12

  The nature of the O-protecting group is crucial to obtain, in terms of diastereoselectivity and chemical yields, the best results. An ab initio molecular orbital study on 2-silyloxy propanal and MM2 studies on 2-alkoxy propanal show the existence of stable cyclic and acyclic conformers, which are presumably responsible for the high syn diastereoselectivity observed in the addition of non-metal carrying

  从手性醛开始已经获得了经由有机亚磷酸酯对醛的不对称膦酰化进行立体控制。就非对映选择性和化学产率而言，O-保护基团的性质对于获得最佳结果至关重要。一个从头算分子轨道研究2甲硅烷氧基丙醛和MM2研究上的2-烷氧基丙醛显示稳定环状和无环的构象，这大概是负责高的存在顺式在加入非承载的金属亚磷酸酯的非对映选择性观察。
• Simultaneous Control of Regio- and Stereochemistries in the Reaction between α-Alkoxyaldehydes and Pentadienyltin. Selective Preparations of the Four Regio- and Diastereoisomers
  作者：Yutaka Nishigaichi、Yasushi Hanano、Akio Takuwa

  DOI：10.1246/cl.1998.33

  日期：1998.1

  In the reaction between α-alkoxyaldehydes and pentadienyltin. each of the possible four regio- and stereoisomers, syn-γ-, anti-γ-, syn-e-, and anti-e-adducts, was selectively synthesized by the use of an appropriate combination of alkoxyl groups, Lewis acids, and solvents applied.

  在α-烷氧基醛和戊二烯基锡之间的反应中。四种可能的区域和立体异构体（syn-γ-、anti-γ-、syn-e- 和 anti-e-加合物）中的每一种都是通过使用适当的烷氧基、路易斯酸和应用的溶剂。
• Addition of Allylindium Reagents to Aldehydes Substituted at C_α or C_β with Heteroatomic Functional Groups. Analysis of the Modulation in Diastereoselectivity Attainable in Aqueous, Organic, and Mixed Solvent Systems
  作者：Leo A. Paquette、Thomas M. Mitzel

  DOI：10.1021/ja953682c

  日期：1996.1.1

  The stereochemical course of indium-promoted allylations to alpha- and beta-oxy aldehydes has been investigated in solvents ranging from anhydrous THF to pure H2O. The free hydroxyl derivatives react with excellent diastereofacial control to give significantly heightened levels of syn-1,2-diols and anti-1,3-diols. Relative reactivities were determined in the alpha-series, and the hydroxy aldehyde proved to be the most reactive substrate. This reactivity ordering suggests that the selectivity stems from chelated intermediates. The rate acceleration observed in water can be heightened by initial acidification. Indeed, the indium-promoted allylation reaction mixtures become increasingly acidic on their own. Preliminary attention has been accorded to salt effects, and tetraethylammonium bromide was found to exhibit a positive synergistic effect on product distribution. Finally, mechanistic considerations are presented in order to allow for assessment of the status of these unprecedented developments at this stage of advancement of the field.