(2E,6E,4S,5S)-4,5,8-Tris((tert-butyldimethylsilyl)oxy)-2,6-octadienal | 165592-64-3

• 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)-4,5,8-Tris((tert-butyldimethylsilyl)oxy)-2,6-octadienal
• 英文别名: (2E,4S,5S,6E)-4,5,8-tris[[tert-butyl(dimethyl)silyl]oxy]octa-2,6-dienal
• CAS: 165592-64-3
• 化学式: C₂₆H₅₄O₄Si₃
• 分子量: 514.969
• InChiKey: BRCAFDOEXUPKGT-CHCWKLOASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.1
• 重原子数：
  33
• 可旋转键数：
  14
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.81
• 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：

  (S)-(Z)-1-(Methoxymethoxy)-3-(tri-n-butylstannyl)-1-butene 、 (2E,6E,4S,5S)-4,5,8-Tris((tert-butyldimethylsilyl)oxy)-2,6-octadienal 在 三氟化硼乙醚 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 以90%的产率得到(2E,6E,10E,4R,5R,8S,9S)-8,9,12-Tris((tert-butyldimethylsilyl)oxy)-4-((methoxymethyl)oxy)-2,6,10-dodecatrien-5-ol
  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
• 作为产物：
  描述：

  Diethyl (4S,5S)-4,5-bis(tert-butyldimethylsiloxy)-2E,6E-octadienedioate 在 正丁基锂 、 草酰氯 、 二异丁基氢化铝 、 二甲基亚砜 、 三乙胺 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 8.17h， 生成 (2E,6E,4S,5S)-4,5,8-Tris((tert-butyldimethylsilyl)oxy)-2,6-octadienal
  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.