(+)-(1S,2S)-2-(2-phenylethyl)cyclopropylmethanol | 142096-79-5

• 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: (+)-(1S,2S)-2-(2-phenylethyl)cyclopropylmethanol
• 英文别名: [(1S,2S)-2-(2-phenylethyl)cyclopropyl]methanol
• CAS: 142096-79-5
• 化学式: C₁₂H₁₆O
• 分子量: 176.258
• InChiKey: NKYZJKZTWSYBTN-NWDGAFQWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  (2E)-5-phenyl-2-pentenal 在 硝酸铵 、 sodium tetrahydroborate 、 diethylzinc 、 4-甲基苯磺酸吡啶 、 溶剂黄146 作用下， 以 乙醇 、 正己烷 、 1,2-二氯乙烷 、 苯 为溶剂， 反应 72.25h， 生成 (+)-(1S,2S)-2-(2-phenylethyl)cyclopropylmethanol
  参考文献：
  名称：

  Asymmetric Cyclopropanation Using New Chiral Auxiliaries Derived from D-Fructose

  摘要：

  Acetals of alpha,beta-unsaturated aldehydes with 3-O-alkylated derivatives of 1,2-O-isopropylidene-beta-D-fructopyranose and 1,2-O-isopropylidene-beta-D-psicopyranose, which are readily available from D-fructose, were cyclopropanated with Et(2)Zn and CH2I2 with good diastereoselectivity. The effects of structure of the acetals on enantioselectivity were examined.

  DOI：

  10.1021/jo00108a018

文献信息

• <i>N</i>,<i>N</i>,<i>N</i>′,<i>N</i>′-Tetraalkyl-2,2′-dihydroxy-1,1′-binaphthyl-3,3′-dicarboxamides: Novel Chiral Auxiliaries for Asymmetric Simmons–Smith Cyclopropanation of Allylic Alcohols and for Asymmetric Diethylzinc Addition to Aldehydes
  作者：Hiroshi Kitajima、Katsuji Ito、Yuko Aoki、Tsutomu Katsuki

  DOI：10.1246/bcsj.70.207

  日期：1997.1

  efficient chiral auxiliaries for the asymmetric Simmons–Smith cyclopropanation of allylic alcohols and for asymmetric addition of diethylzinc to aldehydes. For example, Simmons-Smith cyclopropanation of cinnamyl alcohol in the presence of N,N,N′,N′-tetraethyl-2,2′-dihydroxy-1,1′-binaphthyl-3,3′-dicarboxamide (1b) proceeded with high enantioselectivity of 94% ee and addition of diethylzinc to benzaldehyde

  发现新引入的标题化合物是烯丙醇的不对称 Simmons-Smith 环丙烷化和二乙基锌与醛的不对称加成的有效手性助剂。例如，在 N,N,N',N'-tetraethyl-2,2'-dihydroxy-1,1'-binaphthyl-3,3'-dicarboxamide (1b) 存在下肉桂醇的 Simmons-Smith 环丙烷化反应进行在 N,N,N',N'-四异丙基-2,2'-二羟基-1,1'-联萘-3,3'-二甲酰胺存在下，具有 94% ee 的高对映选择性和二乙基锌与苯甲醛的加成（ 1e) 以 99% ee 的对映选择性进行。尽管这些反应的反应机理仍然是核反应，但单体七元 2,2'-二羟基-1,1'-联萘-3,3'-二甲酰胺 (1)-Zn 复合物被认为是一种活性物质，催化上述反应，
• Catalytic Asymmetric Cyclopropanation of Allylic Alcohols with Titanium-TADDOLate:  Scope of the Cyclopropanation Reaction
  作者：André B. Charette、Carmela Molinaro、Christian Brochu

  DOI：10.1021/ja0108382

  日期：2001.12.1

  titanium-TADDOLate complex was effective at catalyzing the cyclopropanation reaction of allylic alcohols in the presence 1 equiv of bis(iodomethyl)zinc. After initial optimization of the catalyst structure, excellent yields and enantiomeric ratios were obtained for 3-aryl- or 3-heteroaryl-substituted allylic alcohols (up to 97:3). Alkyl-substituted allylic alcohols gave modest yields and enantiomeric ratios (up

  在 1 当量的双（碘甲基）锌存在下，亚化学计量的钛-TADDOLate 络合物可有效催化烯丙醇的环丙烷化反应。在对催化剂结构进行初步优化后，3-芳基-或3-杂芳基-取代的烯丙醇（高达97:3）获得了优异的产率和对映体比率。烷基取代的烯丙醇的产率和对映体比例适中（高达 87:13），但与其他亚化学计量手性配体观察到的相比，这些更有利。本文介绍了该反应的完整合成范围。
• Enantioselective Cyclopropanation of Allylic Alcohols with Dioxaborolane Ligands:  Scope and Synthetic Applications
  作者：André B. Charette、Hélène Juteau、Hélène Lebel、Carmela Molinaro

  DOI：10.1021/ja982055v

  日期：1998.11.1

  the conversion of allylic alcohols into the corresponding enantiomerically enriched cyclopropanes using bis(iodomethyl)zinc. A variety of chiral, nonracemic cyclopropylmethanols could be obtained according to this method. This methodology was extended with success to the cyclopropanation of unconjugated and conjugated polyenes and homoallylic alcohols. The cyclopropanation of allylic carbamates has also

  已发现一种非常有效的手性控制剂，可使用双（碘甲基）锌将烯丙醇转化为相应的富含对映异构体的环丙烷。根据该方法可以获得多种手性、非外消旋环丙基甲醇。该方法成功地扩展到非共轭和共轭多烯和高烯丙醇的环丙烷化。烯丙基氨基甲酸酯的环丙烷化也已用该系统进行了研究，但发现富含对映体的环丙基甲基胺最好由富含对映体的环丙基甲醇制备。
• A new chiral disulfonamide ligand derived from α-amino acid for catalytic enantioselective cyclopropanation
  作者：Nobuyuki Imai、Katsumasa Sakamoto、Masahiro Maeda、Kazushi Kouge、Kenji Yoshizane、Junzo Nokami

  DOI：10.1016/s0040-4039(97)00038-5

  日期：1997.2

  A new disulfonamide prepared from α-amino acid in five steps catalyzed cyclopropanation of allylic alcohols with Et2Zn and CH2I2 to afford the corresponding cyclopropylmethanols in moderate to good enantioselectivites. In particular, the reaction of cinnamyl alcohol in the presence of a chiral disulfonamide 1 k afforded an excellent enantioselectivity (85% ee).

  由α-氨基酸在五个步骤中制备的新的二磺酰胺催化烯丙基醇与Et 2 Zn和CH 2 I 2的环丙烷化，得到相应的环丙基甲醇，为中等至良好的对映体选择性。特别地，肉桂醇在手性二磺酰胺1k的存在下的反应提供了优异的对映选择性（85％ee）。
• A catalytic enantioselective reaction using a C-symmetric disulfonamide as a chiral ligand: Simmons-Smith cyclopropanation of allylic alcohols by the Et2Zn-CH2I2-disulfonamide system
  作者：Hideyo Takahashi、Masato Yoshioka、Masakatsu Shibasaki、Masaji Ohno、Nobuyuki Imai、Susumu Kobayashi

  DOI：10.1016/0040-4020(95)00760-6

  日期：1995.10

  A catalytic and enantioselective Simmons-Smith Cyclopropanation of an allylic alcohol was developed by the reaction of an allylic alcohol with Et2Zn and CH2I2 in the presence of a catalytic amount of chiral disulfonamide 4.

  在催化量的手性二磺酰胺4的存在下，通过烯丙基醇与Et 2 Zn和CH 2 I 2的反应，开发了烯丙基醇的催化和对映选择性席梦思-史密斯环丙烷化反应。