(2E,6E,4S,5S)-4,5-Bis((tert-butyldimethylsilyl)oxy)-2,6-octadiene-1,8-diol | 147227-06-3

• 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: (2E,6E,4S,5S)-4,5-Bis((tert-butyldimethylsilyl)oxy)-2,6-octadiene-1,8-diol
• 英文别名: (2E,4S,5S,6E)-4,5-bis[[tert-butyl(dimethyl)silyl]oxy]octa-2,6-diene-1,8-diol
• CAS: 147227-06-3
• 化学式: C₂₀H₄₂O₄Si₂
• 分子量: 402.722
• InChiKey: PWCMNVQJAFGGOC-KGMIGHOGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.86
• 重原子数：
  26
• 可旋转键数：
  11
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  58.9
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (2E,6E,4S,5S)-4,5-Bis((tert-butyldimethylsilyl)oxy)-2,6-octadiene-1,8-diol 在 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) 、 4 A molecular sieve 、 二异丁基氢化铝 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 8.0h， 生成 (1R,4S)-4-[(1S,2S)-1,2-bis[[tert-butyl(dimethyl)silyl]oxy]-2-[(1S,4R)-4-hydroxycyclopent-2-en-1-yl]ethyl]cyclopent-2-en-1-ol
  参考文献：
  名称：

  A New Synthetic Route to Nucleosides:  Dissymmetric Construction of a Cyclopentene System by Double [3,3]-Sigmatropic Rearrangement and Double Ring-Closing Metathesis

  摘要：

  [GRAPHICS]The dissymmetric synthesis of a carbocyclic nucleoside was achieved by a novel double [3,3]-sigmatropic rearrangement/double ring-closing metathesis strategy with a high stereoselectivity.

  DOI：

  10.1021/ol040006j
• 作为产物：
  描述：

  Diethyl (4S,5S)-4,5-bis(tert-butyldimethylsiloxy)-2E,6E-octadienedioate 在 二异丁基氢化铝 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 2.0h， 以91%的产率得到(2E,6E,4S,5S)-4,5-Bis((tert-butyldimethylsilyl)oxy)-2,6-octadiene-1,8-diol
  参考文献：
  名称：

  Remote Conformational Bias Effects on Diastereofacial Selectivity in SE2' Additions of .gamma.-Oxygenated Allylic Stannanes to Chiral Enals

  摘要：

  The enal 10 derived from (R,R)-diethyl tartrate shows matched/mismatched characteristics in BF3-promoted additions of the chiral gamma-oxygenated allylic stannanes S1, S2, R1, and R2. Both S2 and S1 afford a single syn adduct 11 and 14 with enal 10, whereas R2 and R1 give mixtures of syn and anti products 12/13 and 15/16. Racemic stannane RS2 affords a 82:18 mixture of syn adducts 11 and 12; RS1 gives the two syn adducts 14 and 15 as a 77:23 mixture. The observed facial bias in these additions is attributed to conformational effects engendered by the vicinal syn OTBS substituents which cause enal 10 to adopt a chair-like conformation. The matched additions proceed by attack on the ''outside'' face of the carbonyl grouping in the s-cis orientation of this chair-like arrangement.

  DOI：

  10.1021/jo00104a047

文献信息

• Remote Conformational Bias Effects on Diastereofacial Selectivity in SE2' Additions of .gamma.-Oxygenated Allylic Stannanes to Chiral Enals
  作者：James A. Marshall、Serge Beaudoin

  DOI：10.1021/jo00104a047

  日期：1994.12

  The enal 10 derived from (R,R)-diethyl tartrate shows matched/mismatched characteristics in BF3-promoted additions of the chiral gamma-oxygenated allylic stannanes S1, S2, R1, and R2. Both S2 and S1 afford a single syn adduct 11 and 14 with enal 10, whereas R2 and R1 give mixtures of syn and anti products 12/13 and 15/16. Racemic stannane RS2 affords a 82:18 mixture of syn adducts 11 and 12; RS1 gives the two syn adducts 14 and 15 as a 77:23 mixture. The observed facial bias in these additions is attributed to conformational effects engendered by the vicinal syn OTBS substituents which cause enal 10 to adopt a chair-like conformation. The matched additions proceed by attack on the ''outside'' face of the carbonyl grouping in the s-cis orientation of this chair-like arrangement.
• A New Synthetic Route to Nucleosides:  Dissymmetric Construction of a Cyclopentene System by Double [3,3]-Sigmatropic Rearrangement and Double Ring-Closing Metathesis
  作者：Zhe Fang、Joon Hee Hong

  DOI：10.1021/ol040006j

  日期：2004.3.1

  [GRAPHICS]The dissymmetric synthesis of a carbocyclic nucleoside was achieved by a novel double [3,3]-sigmatropic rearrangement/double ring-closing metathesis strategy with a high stereoselectivity.