(2S,3S,4S)-(1,4-dimethyl-3-phenylazetidin-2-yl)phenylmethanone | 515824-01-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (2S,3S,4S)-(1,4-dimethyl-3-phenylazetidin-2-yl)phenylmethanone
• 英文别名: Methanone, [(2S,3S,4S)-1,4-dimethyl-3-phenyl-2-azetidinyl]phenyl-；[(2S,3S,4S)-1,4-dimethyl-3-phenylazetidin-2-yl]-phenylmethanone
• CAS: 515824-01-8
• 化学式: C₁₈H₁₉NO
• 分子量: 265.355
• InChiKey: RJUMOQXTGROJCL-XKQJLSEDSA-N

物化性质

• 熔点：
  91 °C
• 沸点：
  391.6±42.0 °C(Predicted)
• 密度：
  1.090±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  20
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.28
• 拓扑面积：
  20.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (2S,3S,4S)-(1,4-dimethyl-3-phenylazetidin-2-yl)phenylmethanone 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 2.17h， 生成 (2S,3S,4S)-1,1,4-trimethyl-3-phenyl-2-(1-phenylvinyl)azetidinium trifluoromethanesulfonate
  参考文献：
  名称：

  2-烯基氮杂环丁鎓盐的环膨胀——吡咯烷和氮杂环庚烷的新途径

  摘要：

  从 2-烯基氮杂鎓三氟甲磺酸盐合成了一系列对映体纯 3-烯基吡咯烷、取代的氮杂环庚烷和立体定义的氨基烯烃。发现这些反应的高化学选择性强烈依赖于该过程中所涉及的碱（PhLi 或 KHMDS）的性质以及中间体叶立德铵的相对顺式或反式立体化学。当叶立德和相邻的烯烃是反式时，[1,2] σ 移位仅发生，产生具有高水平区域选择性的吡咯烷。另一方面，当这两个基团处于顺式关系时，观察到通过 [2,3] sigmatropic 转移干净地转化为 4,5-脱氢氮杂环庚烷。（© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany , 2006)

  DOI：

  10.1002/ejoc.200600362
• 作为产物：
  描述：

  (2S,3S,4S)-1,4-dimethyl-3-phenyl-azetidine-2-carbonitrile 在 silica gel 作用下， 以 乙醚 、 环己烷 、 Petroleum ether 、 苯 为溶剂， 反应 0.25h， 生成 (2S,3S,4S)-(1,4-dimethyl-3-phenylazetidin-2-yl)phenylmethanone
  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

• Synthesis and reactivity of enantiomerically pure N-alkyl-2-alkenyl azetidinium salts
  作者：François Couty、François Durrat、Gwilherm Evano、Damien Prim

  DOI：10.1016/j.tetlet.2004.07.113

  日期：2004.9

  A synthesis of stereodefined enantiomerically pure 2-alkenyl azetidines is described using Wittig olefination as key step. The quaternary triflate ammonium salts of these heterocycles were prepared in a stereoselective way and treatment of these azetidinium salts with a base (KHMDS or PhLi) induced a regioselective Stevens rearrangement leading to a 3-alkenyl pyrrolidine. An unprecedented SN2′ reaction

  以维蒂希烯化为关键步骤描述了立体定义的对映体纯的2-烯基氮杂环丁烷的合成。以立体选择性的方式制备这些杂环的季铵盐季铵盐，并用碱（KHMDS或PhLi）处理这些氮杂环丁鎓盐可引起区域选择性的史蒂文斯重排，从而形成3-烯基吡咯烷。在一种情况下，观察到了前所未有的S N 2'反应，其中涉及苯基锂为亲核试剂和铵为离去基团。
• Reaction of Azetidines with Chloroformates
  作者：Monica Vargas-Sanchez、Sami Lakhdar、François Couty、Gwilherm Evano

  DOI：10.1021/ol062128c

  日期：2006.11.1

  The reaction of an azetidine with a chloroformate can give either the dealkylated heterocycle or the ring-opened product (gamma-chloroamine), which can further cyclize to the oxazinanone. A general study of this underrated reaction was conducted and revealed that azetidines can undergo smooth nucleophilic ring-opening reactions to highly functionalized gamma-chloroamines in the presence of a variety of alkyl chloroformates under mild reaction conditions. Yields are usually good, and parameters governing this reaction were evaluated.
• 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.
• Ring Expansions of 2-Alkenylazetidinium Salts – a New Route to Pyrrolidines and Azepanes
  作者：François Couty、François Durrat、Gwilherm Evano、Jérome Marrot

  DOI：10.1002/ejoc.200600362

  日期：2006.9

  Series of enantiomerically pure 3-alkenylpyrrolidines, substituted azepanes and stereodefined aminoalkenes were synthesized from 2-alkenylazetidinium trifluoromethanesulfonate salts. The high chemoselectivity of these reactions was found to be strongly dependent both on the nature of the base involved in the process (PhLi or KHMDS) and on the relative cis or trans stereochemistry of the intermediate

  从 2-烯基氮杂鎓三氟甲磺酸盐合成了一系列对映体纯 3-烯基吡咯烷、取代的氮杂环庚烷和立体定义的氨基烯烃。发现这些反应的高化学选择性强烈依赖于该过程中所涉及的碱（PhLi 或 KHMDS）的性质以及中间体叶立德铵的相对顺式或反式立体化学。当叶立德和相邻的烯烃是反式时，[1,2] σ 移位仅发生，产生具有高水平区域选择性的吡咯烷。另一方面，当这两个基团处于顺式关系时，观察到通过 [2,3] sigmatropic 转移干净地转化为 4,5-脱氢氮杂环庚烷。（© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany , 2006)