(3S,4R)-3-O-tert-butyl-diphenylsilyl-4,5-O-cyclohexylidene-3,4,5-trihydroxy-pentanal | 1197010-63-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (3S,4R)-3-O-tert-butyl-diphenylsilyl-4,5-O-cyclohexylidene-3,4,5-trihydroxy-pentanal
• 英文别名: (3S)-3-[tert-butyl(diphenyl)silyl]oxy-3-[(3R)-1,4-dioxaspiro[4.5]decan-3-yl]propanal
• CAS: 1197010-63-1
• 化学式: C₂₇H₃₆O₄Si
• 分子量: 452.666
• InChiKey: LLLBGOMQWYUWKZ-LOSJGSFVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  32
• 可旋转键数：
  8
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.52
• 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：

  (3S,4R)-3-O-tert-butyl-diphenylsilyl-4,5-O-cyclohexylidene-3,4,5-trihydroxy-pentanal 在 sodium hydride 、 二异丁基氢化铝 、 碳酸氢钠 、 三乙胺 、 sodium bromide 、 锌 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 丙酮 为溶剂， 反应 2.67h， 生成 (5S,6R)-3-hydroxymethyl-5-O-tert-butyl-diphenylsilyl-6,7-O-cyclohexylidene-5,6,7-trihydroxy-hept-1-ene
  参考文献：
  名称：

  Stereodivergent Route to the Carbocyclic Core of 2′,3′-Olefinic Carbanucleosides: Toward the Synthesis of (l)-(+)- and (d)-(−)-Carbovir

  摘要：

  (R)-2,3-Cyclohexylideneglyceraldehyde (1) has been elegantly exploited for a stereodivergent construction of the potential precursors (ha and 11b) of (L)-(+)- and (D)-(-)-carbovirs, respectively. The key steps in this approach were Luche's allylation of formaldehyde with allylic bromide 4c to produce 5 and ring-closing metathesis of 10b using Grubbs' first-generation catalyst to obtain 11. The moderate stereoselectivity of Luche's allylation reaction resulted in attaining stereodivergence in this approach which could be realized finally through easy chromatographic separation of the two isomers of the metathesis product to obtain homochiral precursors ha and lib in good amounts.

  DOI：

  10.1021/jo200670v
• 作为产物：
  描述：

  (2R,3S)-3-tert-butyldiphenylsilyloxy-1,2-(cyclohexylidenedioxy)hex-5-ene 在 臭氧 、 三苯基膦 作用下， 以 二氯甲烷 为溶剂， 生成 (3S,4R)-3-O-tert-butyl-diphenylsilyl-4,5-O-cyclohexylidene-3,4,5-trihydroxy-pentanal
  参考文献：
  名称：

  从（R）-2,3-亚环己基甘油醛到1,3-二醇的简单输入：（-）-没食子酸的合成

  摘要：

  醛5，7和9从容易获得（派生- [R）-2,3- cyclohexylideneglyceraldehyde 1被用作新底物，以获得这两个顺式和-抗由它们中的每经受一些在多个单独的反应-1,3-二醇在潮湿条件下几乎可行的金属介导的Barbier型烯丙基化。在这方面，对与这些醛5-7的四个这种金属介导的烯丙基化相关的相容性和立体选择性进行了详细的研究。。在几个成功的反应中具有良好的收率，具有适度的选择性，并且可以容易地色谱分离产物的非对映异构体，已成功地分离出两对对映体纯的syn -1,3和抗-1,3-二醇（6a和6b；10a和10b） ）。最后，图10b已经被利用来合成（ - ） - galantinic酸甲。

  DOI：

  10.1016/j.tetasy.2009.07.030

文献信息

• A simple entry into 1,3-diols from (R)-2,3-cyclohexylideneglyceraldehyde: synthesis of (−)-galantinic acid
  作者：Bhaskar Dhotare、Angshuman Chattopadhyay

  DOI：10.1016/j.tetasy.2009.07.030

  日期：2009.9

  Aldehydes 5, 7, and 9 derived from easily accessible (R)-2,3-cyclohexylideneglyceraldehyde 1 were used as novel substrates to obtain both syn- and anti-1,3-diols in several individual reactions by subjecting each of them to some practically viable metal-mediated Barbier-type allylations under moist conditions. In this regard, a detailed investigation was made regarding the compatibility and stereoselectivity

  醛5，7和9从容易获得（派生- [R）-2,3- cyclohexylideneglyceraldehyde 1被用作新底物，以获得这两个顺式和-抗由它们中的每经受一些在多个单独的反应-1,3-二醇在潮湿条件下几乎可行的金属介导的Barbier型烯丙基化。在这方面，对与这些醛5-7的四个这种金属介导的烯丙基化相关的相容性和立体选择性进行了详细的研究。。在几个成功的反应中具有良好的收率，具有适度的选择性，并且可以容易地色谱分离产物的非对映异构体，已成功地分离出两对对映体纯的syn -1,3和抗-1,3-二醇（6a和6b；10a和10b） ）。最后，图10b已经被利用来合成（ - ） - galantinic酸甲。
• Stereodivergent Route to the Carbocyclic Core of 2′,3′-Olefinic Carbanucleosides: Toward the Synthesis of (<scp>l</scp>)-(+)- and (<scp>d</scp>)-(−)-Carbovir
  作者：Angshuman Chattopadhyay、Sibanarayan Tripathy

  DOI：10.1021/jo200670v

  日期：2011.7.15

  (R)-2,3-Cyclohexylideneglyceraldehyde (1) has been elegantly exploited for a stereodivergent construction of the potential precursors (ha and 11b) of (L)-(+)- and (D)-(-)-carbovirs, respectively. The key steps in this approach were Luche's allylation of formaldehyde with allylic bromide 4c to produce 5 and ring-closing metathesis of 10b using Grubbs' first-generation catalyst to obtain 11. The moderate stereoselectivity of Luche's allylation reaction resulted in attaining stereodivergence in this approach which could be realized finally through easy chromatographic separation of the two isomers of the metathesis product to obtain homochiral precursors ha and lib in good amounts.