(Z)-2-[(dimethyl-phenyl-silyl)-methylene]-3-hydroxy-3-phenyl-butanal

• 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: (Z)-2-[(dimethyl-phenyl-silyl)-methylene]-3-hydroxy-3-phenyl-butanal
• 英文别名: (Z)-2-(1-hydroxy-1-phenylethyl)-3-dimethylphenylsilylpropenal；(2Z)-2-[[dimethyl(phenyl)silyl]methylidene]-3-hydroxy-3-phenylbutanal
• 化学式: C₁₉H₂₂O₂Si
• 分子量: 310.468
• InChiKey: KPKDOGINPWHTCZ-BMRADRMJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.17
• 重原子数：
  22
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  二甲基苯基硅烷 、 (Z)-2-[(dimethyl-phenyl-silyl)-methylene]-3-hydroxy-3-phenyl-butanal 在 dodecacarbonyltetrarhodium(0) 、 一氧化碳 作用下， 以 苯 为溶剂， 100.0 ℃ 、2.03 MPa 条件下， 反应 7.0h， 生成 (Z)-2-(dimethylphenylsilylmethyl)-3-phenyl-2-butenal 、 (E)-2-(dimethylphenylsilylmethyl)-3-phenyl-2-butenal
  参考文献：
  名称：

  Rhodium-catalyzed transformation of propargyl alcohol derivatives to 2-silylmethyl-2-alkenals

  摘要：

  Propargyl-type alcohols (6) and the corresponding esters of carbonic acid (4) or acetic acid (5) react with two equivalents of Me2PhSiH in the presence of catalytic amounts of Rh-4(CO)(12) under CO pressure at 100 degrees C to give 2-(dimethylphenylsiIylmethyl)-2-alkenals (3), whereas 2-substituted-3-(dimethylphenylsilyl)propenals (7, 8 and 9) are also isolated with the concomitant formation of 3 when a similar reaction is operated with shortage of Me2PhSiH or with lowering of reaction temperature. The isolated 9 is selectively converted to 3 by the Rh-4(CO)(12) catalyzed reaction with Me2PhSiH under CO pressure. This fact suggests that the transformation of 4, 5 or 6 to 3 is accomplished by either a one-pot procedure or a stepwise procedure relayed by 7, 8 or 9. Usefulness of this protocol is demonstrated by the synthesis of 18 in which ethisterone (17) is directly converted by a one-pot procedure. (C) 1999 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0022-328x(98)00933-4
• 作为产物：
  描述：

  2-苯基-3-丁炔-2-醇 、 一氧化碳 、 二甲基苯基硅烷 在 dodecacarbonyltetrarhodium(0) 作用下， 以 二氯甲烷 为溶剂， 20.0 ℃ 、3.04 MPa 条件下， 反应 24.0h， 以55%的产率得到(Z)-2-[(dimethyl-phenyl-silyl)-methylene]-3-hydroxy-3-phenyl-butanal
  参考文献：
  名称：

  通过炔丙醇的甲硅烷基碳环化/去甲硅烷基化反应合成功能化的β-内酯

  摘要：

  通过有效的铑催化的甲硅烷基碳环化反应，从炔丙基醇开始制备官能化的β-内酯。使用DBU作为碱，位阻醇和/或氢硅烷，可以高收率和完全的立体选择性进行此过程。否则，发生甲硅烷基甲酰化竞争反应，得到具有完全区域选择性的3-羟基-2-[（芳基二甲基甲硅烷基）亚甲基]烷基。确实，尽管α-（芳基二甲基甲硅烷基亚甲基）-β-内酯仅从炔丙基碳原子上具有两个烷基的炔醇开始生成，但对于仲醇却观察到大量的醛。在这些情况下，使用邻位取代的芳基硅烷改善了对α-亚甲基-β-内酯的化学选择性。然后，这些分子通过氟化物诱导的芳基的重排成功地转化为α-甲基芳基-β-内酯，芳基从硅迁移到碳并保留构型。

  DOI：

  10.1016/j.tet.2009.10.112

文献信息

• Rhodium-catalyzed transformation of propargyl alcohol derivatives to 2-silylmethyl-2-alkenals
  作者：Isamu Matsuda、Nakayoshi Niikawa、Rika Kuwabara、Hirofumi Inoue、Hideo Nagashima、Kenji Itoh

  DOI：10.1016/s0022-328x(98)00933-4

  日期：1999.2

  Propargyl-type alcohols (6) and the corresponding esters of carbonic acid (4) or acetic acid (5) react with two equivalents of Me2PhSiH in the presence of catalytic amounts of Rh-4(CO)(12) under CO pressure at 100 degrees C to give 2-(dimethylphenylsiIylmethyl)-2-alkenals (3), whereas 2-substituted-3-(dimethylphenylsilyl)propenals (7, 8 and 9) are also isolated with the concomitant formation of 3 when a similar reaction is operated with shortage of Me2PhSiH or with lowering of reaction temperature. The isolated 9 is selectively converted to 3 by the Rh-4(CO)(12) catalyzed reaction with Me2PhSiH under CO pressure. This fact suggests that the transformation of 4, 5 or 6 to 3 is accomplished by either a one-pot procedure or a stepwise procedure relayed by 7, 8 or 9. Usefulness of this protocol is demonstrated by the synthesis of 18 in which ethisterone (17) is directly converted by a one-pot procedure. (C) 1999 Elsevier Science S.A. All rights reserved.
• Synthesis of functionalised β-lactones via silylcarbocyclisation/desilylation reactions of propargyl alcohols
  作者：Laura Antonella Aronica、Caterina Mazzoni、Anna Maria Caporusso

  DOI：10.1016/j.tet.2009.10.112

  日期：2010.1

  alkynol characterised by two alkyl groups on the propargyl carbon atom, significant amounts of the aldehydes were observed for secondary alcohols. In these cases, the use of ortho-substituted arylsilanes improved the chemoselectivity towards the α-methylene-β-lactones. Such molecules were then successfully converted into α-methylaryl-β-lactones by a fluoride-induced rearrangement of the aryl group that migrates

  通过有效的铑催化的甲硅烷基碳环化反应，从炔丙基醇开始制备官能化的β-内酯。使用DBU作为碱，位阻醇和/或氢硅烷，可以高收率和完全的立体选择性进行此过程。否则，发生甲硅烷基甲酰化竞争反应，得到具有完全区域选择性的3-羟基-2-[（芳基二甲基甲硅烷基）亚甲基]烷基。确实，尽管α-（芳基二甲基甲硅烷基亚甲基）-β-内酯仅从炔丙基碳原子上具有两个烷基的炔醇开始生成，但对于仲醇却观察到大量的醛。在这些情况下，使用邻位取代的芳基硅烷改善了对α-亚甲基-β-内酯的化学选择性。然后，这些分子通过氟化物诱导的芳基的重排成功地转化为α-甲基芳基-β-内酯，芳基从硅迁移到碳并保留构型。