(2S,3S)-3-isopropyl-2-phenyl-2,3-epoxypropan-1-triphenylsilyl ether | 350795-04-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (2S,3S)-3-isopropyl-2-phenyl-2,3-epoxypropan-1-triphenylsilyl ether
• 英文别名: triphenyl-[[(2S,3S)-2-phenyl-3-propan-2-yloxiran-2-yl]methoxy]silane
• CAS: 350795-04-9
• 化学式: C₃₀H₃₀O₂Si
• 分子量: 450.653
• InChiKey: PNLZRQWHVWISSR-XZWHSSHBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.62
• 重原子数：
  33
• 可旋转键数：
  8
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  21.8
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (2S,3S)-3-isopropyl-2-phenyl-2,3-epoxypropan-1-triphenylsilyl ether 在 palladium on activated charcoal lithium aluminium tetrahydride 、 pyridine-SO3 complex 、 盐酸羟胺 、 四丁基氟化铵 、 氢气 、 sodium acetate 、 甲铝双(2,6-二叔丁基-4-苯甲醚) 、 sodium hydride 、 三乙胺 、 N,N'-羰基二咪唑 作用下， 以 四氢呋喃 、 乙醇 、 二氯甲烷 、 二甲基亚砜 、 乙酸乙酯 、 甲苯 为溶剂， -78.0~20.0 ℃ 、101.33 kPa 条件下， 反应 29.0h， 生成 (2S)-2-(2-isopropyl)-5-hydroxy-2-phenylpentanenitrile
  参考文献：
  名称：

  Practical Synthesis of Chiral Emopamil Left Hand as a Bioactive Motif

  摘要：

  An asymmetric synthesis of (2S)-2-(2-isopropyl)-5-hydroxy-2-phenylpentanenitrile (emopamil left hand, 2) has been completed by use of the MAD (methyl aluminum bis(4-methyl-2,6-di-tert-butylphenoxide)-induced rearrangement of a chiral epoxyalcohol as the key reaction. The stereochemistry of the chiral quaternary center was confirmed by transformation of 2 to (S)-noremopamil. This method requires minimal purification procedures and affords high chemical and optical yields. Acid-catalyzed isomerization of an allylaldehyde and retro-aldol type racemization at the quaternary carbon of a nitrile-alcohol were encountered.

  DOI：

  10.1021/jo020166d
• 作为产物：
  描述：

  4-methyl-2-phenylpent-2-en-1-ol 在 叔丁基过氧化氢 咪唑 、 titanium(IV) isopropylate 、 L-(+)-酒石酸二乙酯 、 4 A molecular sieve 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 21.0h， 生成 (2S,3S)-3-isopropyl-2-phenyl-2,3-epoxypropan-1-triphenylsilyl ether
  参考文献：
  名称：

  Practical Synthesis of Chiral Emopamil Left Hand as a Bioactive Motif

  摘要：

  An asymmetric synthesis of (2S)-2-(2-isopropyl)-5-hydroxy-2-phenylpentanenitrile (emopamil left hand, 2) has been completed by use of the MAD (methyl aluminum bis(4-methyl-2,6-di-tert-butylphenoxide)-induced rearrangement of a chiral epoxyalcohol as the key reaction. The stereochemistry of the chiral quaternary center was confirmed by transformation of 2 to (S)-noremopamil. This method requires minimal purification procedures and affords high chemical and optical yields. Acid-catalyzed isomerization of an allylaldehyde and retro-aldol type racemization at the quaternary carbon of a nitrile-alcohol were encountered.

  DOI：

  10.1021/jo020166d

文献信息

• Metallophthalocyanine complex, Cr(TBPC)OTf: an efficient, recyclable Lewis acid catalyst in the regio- and stereoselective rearrangement of epoxides to aldehydes
  作者：Kohji Suda、Shin-ichiro Nakajima、Yasumi Satoh、Toshikatsu Takanami

  DOI：10.1039/b820948k

  日期：——

  The metallophthalocyanine complex Cr(TBPC)OTf works as a highly efficient, recyclable Lewis acid catalyst for the regio- and stereoselective rearrangements of epoxides to aldehydes.

  金属酞菁配合物Cr（TBPC）OTf是高效，可回收的路易斯酸催化剂，用于环氧化物和立体选择性重排成醛。
• Highly Regio- and Stereoselective Rearrangement of Epoxides to Aldehydes Catalyzed by High-Valent Metalloporphyrin Complex, Cr(TPP)OTf
  作者：Kohji Suda、Taketoshi Kikkawa、Shin-ichiro Nakajima、Toshikatsu Takanami

  DOI：10.1021/ja047104k

  日期：2004.8.1

  characteristic Lewis acid catalyst in the regio- and stereoselective rearrangement of epoxides to aldehydes. This Cr(TPP)OTf-catalyzed reaction is an operationally simple and especially convenient method for synthesizing optically active beta-siloxy aldehydes from 2,3-epoxy silyl ethers which are readily available in enantiomerically enriched forms by the Sharpless epoxidation of allylic alcohols followed

  三氟甲磺酸铬 (III) 四苯基卟啉三氟甲磺酸盐 Cr(TPP)OTf 在环氧化物向醛的区域和立体选择性重排中作为一种有效且具有特征性的路易斯酸催化剂起作用。这种 Cr(TPP)OTf 催化的反应是一种操作简单且特别方便的方法，用于从 2,3-环氧甲硅烷基醚合成光学活性 β-甲硅烷氧基醛，这些乙丙醚​​很容易通过烯丙醇的 Sharpless 环氧化以富含对映体的形式获得硅烷化。
• Practical Synthesis of Chiral Emopamil Left Hand as a Bioactive Motif
  作者：Teiji Kimura、Noboru Yamamoto、Yuichi Suzuki、Koki Kawano、Yoshihiko Norimine、Koichi Ito、Satoshi Nagato、Yoichi Iimura、Masahiro Yonaga

  DOI：10.1021/jo020166d

  日期：2002.8.1

  An asymmetric synthesis of (2S)-2-(2-isopropyl)-5-hydroxy-2-phenylpentanenitrile (emopamil left hand, 2) has been completed by use of the MAD (methyl aluminum bis(4-methyl-2,6-di-tert-butylphenoxide)-induced rearrangement of a chiral epoxyalcohol as the key reaction. The stereochemistry of the chiral quaternary center was confirmed by transformation of 2 to (S)-noremopamil. This method requires minimal purification procedures and affords high chemical and optical yields. Acid-catalyzed isomerization of an allylaldehyde and retro-aldol type racemization at the quaternary carbon of a nitrile-alcohol were encountered.