(1'R,2S,3S,4S)-(1,4-dimethyl-3-phenylazetidin-2-yl)phenylmethanol | 515824-05-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氮杂环丁烷
• 英文名称: (1'R,2S,3S,4S)-(1,4-dimethyl-3-phenylazetidin-2-yl)phenylmethanol
• 英文别名: (R)-[(2S,3S,4S)-1,4-dimethyl-3-phenylazetidin-2-yl]-phenylmethanol
• CAS: 515824-05-2
• 化学式: C₁₈H₂₁NO
• 分子量: 267.371
• InChiKey: AJUYRACKRWQXSR-HNONPPJISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  20
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  23.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1'R,2S,3S,4S)-(1,4-dimethyl-3-phenylazetidin-2-yl)phenylmethanol 在 甲基磺酰氯 、 三乙胺 作用下， 以77%的产率得到(2S,3S,4S,5S)-3-Chloro-1,5-dimethyl-2,4-diphenyl-pyrrolidine
  参考文献：
  名称：

  对映体纯α-羟烷基氮杂环丁烷的立体选择性高扩环

  摘要：

  由对映体纯的β-氨基醇经几个步骤制得的立体定义的α-羟烷基氮杂环丁烷被氯化或以良好的产率转化为甲磺酰氧基甲基衍生物。在氯仿或二甲基甲酰胺中加热这些化合物可引起立体有择的环扩大，从而产生3-氯或3-甲磺酰氧基吡咯烷。这种重排的容易性取决于所述迁移基团的性质（CL -或MSO - ），类起始醇的和起始材料的相对立体化学的（初级或次级）。

  DOI：

  10.1016/s0040-4039(03)01227-9
• 作为产物：
  描述：

  (2S,3S,4S)-1,4-dimethyl-3-phenyl-azetidine-2-carbonitrile 在 sodium tetrahydroborate 、 silica gel 作用下， 以 乙醚 、 乙醇 、 环己烷 、 Petroleum ether 、 苯 为溶剂， 反应 1.75h， 生成 (1'R,2S,3S,4S)-(1,4-dimethyl-3-phenylazetidin-2-yl)phenylmethanol
  参考文献：
  名称：

  Synthesis of enantiopure 2-acyl azetidines and the application of amino alcohols derived therefrom in enantioselective catalysis

  摘要：

  Enantiopure 2-acyl azetidines were prepared in good yields from 2-cyano azetidines. The ketones produced were then stereo selectively reduced with sodium borohydride (with or without zinc bromide) or transformed into tertiary azetidinic amino alcohols by addition of phenyllithium. The latter compounds were found to be highly efficient catalysts for the enantioselective addition of diethylzinc to aldehydes, giving enantioselectivities up to 98%. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(02)00710-3

文献信息

• Rearrangement of 2-Hydroxyalkylazetidines into 3-Fluoropyrrolidines
  作者：François Couty、Bruno Drouillat、Olivier David、Gwilherm Evano、Jérome Marrot

  DOI：10.1055/s-2008-1072770

  日期：2008.5

  Upon treatment with DAST (diethylaminosulfur trifluoride) enantiopure 2-hydroxyalkylazetidines rearrange into 3-fluoropyrrolidines. The reaction is stereospecific and involves a bicyclic 1-azoniabicyclo[2.1.0]pentane intermediate which is regioselectively opened by a fluoride anion.

  用 DAST（二乙氨基三氟化硫）处理后，对映体纯的 2-羟基烷基氮杂环丁烷重排为 3-氟吡咯烷。该反应是立体有择的，涉及双环 1-azoniabicyclo[2.1.0] 戊烷中间体，该中间体被氟阴离子区域选择性地打开。
• Ring Expansion of 2‐(α‐Hydroxyalkyl)azetidines: A Synthetic Route to Functionalized Pyrrolidines
  作者：François Durrat、Monica Vargas Sanchez、François Couty、Gwilherm Evano、Jérôme Marrot

  DOI：10.1002/ejoc.200800316

  日期：2008.7

  A series of 2-(α-hydroxyalkyl)azetidines synthesized from enantiomerically pure β-amino alcohols and presenting various patterns both on the four-membered ring and on the adjacent hydroxy group were treated with either thionyl chloride or methanesulfonyl chloride in the presence of triethylamine. The thus-prepared 2-(α-chloro- or α-methanesulfonyloxyalkyl)azetidines were shown to rearrange stereospecifically

  在三乙胺存在下，用亚硫酰氯或甲磺酰氯处理由对映体纯 β-氨基醇合成的一系列 2-（α-羟烷基）氮杂环丁烷，并在四元环和相邻羟基上呈现各种模式. 如此制备的 2-(α-氯-或 α-甲磺酰氧基烷基) 氮杂环丁烷显示立体定向重排成 3-(氯-或甲磺酰氧基) 吡咯烷。当这种重排在添加的亲核试剂（NaN3、KCN、KOH 或 NaOAc）存在下进行时，产生的吡咯烷会在 C-3 立体特异性地结合添加的亲核试剂。形成的吡咯烷中取代基的相对构型与中间体双环氮丙啶离子形成的机制一致，它在桥头碳原子上区域选择性地打开。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)
• Highly stereoselective ring expansion of enantiopure α-hydroxyalkyl azetidines
  作者：François Couty、François Durrat、Damien Prim

  DOI：10.1016/s0040-4039(03)01227-9

  日期：2003.7

  α-hydroxyalkyl azetidines, prepared in a few steps from enantiopure β-amino alcohols, are chlorinated or transformed into methanesulfonyloxymethyl derivatives in good yields. Heating of these compounds in chloroform or dimethylformamide induces a stereospecific ring enlargement to give 3-chloro or 3-methanesulfonyloxy pyrrolidines. The ease of this rearrangement depends on the nature of the migrating

  由对映体纯的β-氨基醇经几个步骤制得的立体定义的α-羟烷基氮杂环丁烷被氯化或以良好的产率转化为甲磺酰氧基甲基衍生物。在氯仿或二甲基甲酰胺中加热这些化合物可引起立体有择的环扩大，从而产生3-氯或3-甲磺酰氧基吡咯烷。这种重排的容易性取决于所述迁移基团的性质（CL -或MSO - ），类起始醇的和起始材料的相对立体化学的（初级或次级）。
• Synthesis of enantiopure 2-acyl azetidines and the application of amino alcohols derived therefrom in enantioselective catalysis
  作者：François Couty、Damien Prim

  DOI：10.1016/s0957-4166(02)00710-3

  日期：2002.11

  Enantiopure 2-acyl azetidines were prepared in good yields from 2-cyano azetidines. The ketones produced were then stereo selectively reduced with sodium borohydride (with or without zinc bromide) or transformed into tertiary azetidinic amino alcohols by addition of phenyllithium. The latter compounds were found to be highly efficient catalysts for the enantioselective addition of diethylzinc to aldehydes, giving enantioselectivities up to 98%. (C) 2002 Elsevier Science Ltd. All rights reserved.