(1'R,2R,5R,6R)-5-{1'-[(2-bromophenyl)sulfanyl]-3'-phenylpropyl}-2-tert-butyl-6-methyl-1,3-dioxan-4-one | 334816-41-0

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: (1'R,2R,5R,6R)-5-{1'-[(2-bromophenyl)sulfanyl]-3'-phenylpropyl}-2-tert-butyl-6-methyl-1,3-dioxan-4-one
• 英文别名: (2R,5R,6R)-5-[(1R)-1-(2-bromophenyl)sulfanyl-3-phenylpropyl]-2-tert-butyl-6-methyl-1,3-dioxan-4-one
• CAS: 334816-41-0
• 化学式: C₂₄H₂₉BrO₃S
• 分子量: 477.462
• InChiKey: MKTBEYBLOUKSBM-BMWHPICZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.3
• 重原子数：
  29
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  60.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (1'R,2R,5R,6R)-5-{1'-[(2-bromophenyl)sulfanyl]-3'-phenylpropyl}-2-tert-butyl-6-methyl-1,3-dioxan-4-one 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 以73%的产率得到(+)-(1'R,2R,3R)-3-[1'-hydroxyethyl]-2-phenylethylthiochroman-4-one
  参考文献：
  名称：

  Stereoselective Synthesis of Thiochroman-4-ones by Ring Transformation of Chiral 5-Ylidene-1,3-dioxan-4-ones with 2-Bromothiophenol via Bromo−Lithium Exchange

  摘要：

  The reaction of (E)- or (Z)-5-ylidene-1,3-dioxan-4-one (1) and 2-bromothiophenol, followed by bromo-lithium exchange with nBuLi, provides a new access to optically active thiochroman-4-ones 4 and 5. Stereoselective conjugate addition occurs in the first step and the resulting 5-(1-phenylsulfanylalkyl)-1,3-dioxan-4-ones 2 and 3 undergo ring transformation to thiochroman-4-ones by attack of the lithiated phenyl ring at the dioxanone carbonyl carbon atom, cleaving off pivalaldehyde. If reactants with a (Z)-configuration are used, a retro-aldol reaction occurs in the ring transformation step, thus affording the 3-unsubstituted thiochroman-4-ones 5 rather than 3-(l-hydroxyethyl)-thiochroman-4-ones 4. This phenomenon can be rationalized by the steric congestion in the intermediate enolate 7.

  DOI：

  10.1002/1099-0690(200102)2001:3<529::aid-ejoc529>3.0.co;2-b
• 作为产物：
  描述：

  2-溴硫代苯酚 、 (2R,6R)-2-(tert-Butyl)-6-methyl-5-[(E)-3-phenylpropylidene]-1,3-dioxan-4-one 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 以83%的产率得到(1'R,2R,5R,6R)-5-{1'-[(2-bromophenyl)sulfanyl]-3'-phenylpropyl}-2-tert-butyl-6-methyl-1,3-dioxan-4-one
  参考文献：
  名称：

  Stereoselective Synthesis of Thiochroman-4-ones by Ring Transformation of Chiral 5-Ylidene-1,3-dioxan-4-ones with 2-Bromothiophenol via Bromo−Lithium Exchange

  摘要：

  The reaction of (E)- or (Z)-5-ylidene-1,3-dioxan-4-one (1) and 2-bromothiophenol, followed by bromo-lithium exchange with nBuLi, provides a new access to optically active thiochroman-4-ones 4 and 5. Stereoselective conjugate addition occurs in the first step and the resulting 5-(1-phenylsulfanylalkyl)-1,3-dioxan-4-ones 2 and 3 undergo ring transformation to thiochroman-4-ones by attack of the lithiated phenyl ring at the dioxanone carbonyl carbon atom, cleaving off pivalaldehyde. If reactants with a (Z)-configuration are used, a retro-aldol reaction occurs in the ring transformation step, thus affording the 3-unsubstituted thiochroman-4-ones 5 rather than 3-(l-hydroxyethyl)-thiochroman-4-ones 4. This phenomenon can be rationalized by the steric congestion in the intermediate enolate 7.

  DOI：

  10.1002/1099-0690(200102)2001:3<529::aid-ejoc529>3.0.co;2-b

文献信息

• Stereoselective Synthesis of Thiochroman-4-ones by Ring Transformation of Chiral 5-Ylidene-1,3-dioxan-4-ones with 2-Bromothiophenol via Bromo−Lithium Exchange
  作者：Akbar Ali、Viqar Uddin Ahmad、Jürgen Liebscher

  DOI：10.1002/1099-0690(200102)2001:3<529::aid-ejoc529>3.0.co;2-b

  日期：2001.2

  The reaction of (E)- or (Z)-5-ylidene-1,3-dioxan-4-one (1) and 2-bromothiophenol, followed by bromo-lithium exchange with nBuLi, provides a new access to optically active thiochroman-4-ones 4 and 5. Stereoselective conjugate addition occurs in the first step and the resulting 5-(1-phenylsulfanylalkyl)-1,3-dioxan-4-ones 2 and 3 undergo ring transformation to thiochroman-4-ones by attack of the lithiated phenyl ring at the dioxanone carbonyl carbon atom, cleaving off pivalaldehyde. If reactants with a (Z)-configuration are used, a retro-aldol reaction occurs in the ring transformation step, thus affording the 3-unsubstituted thiochroman-4-ones 5 rather than 3-(l-hydroxyethyl)-thiochroman-4-ones 4. This phenomenon can be rationalized by the steric congestion in the intermediate enolate 7.