2-Nitro-3-phenethyl-2-p-tolylsulfanyl-oxirane | 168135-87-3

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: 2-Nitro-3-phenethyl-2-p-tolylsulfanyl-oxirane
• 英文别名: 2-(4-Methylphenyl)sulfanyl-2-nitro-3-(2-phenylethyl)oxirane
• CAS: 168135-87-3
• 化学式: C₁₇H₁₇NO₃S
• 分子量: 315.393
• InChiKey: ATOGLUJECGTHCY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  22
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  83.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2-Nitro-3-phenethyl-2-p-tolylsulfanyl-oxirane 在 ammonium hydroxide 作用下， 以 二氯甲烷 为溶剂， 生成 2-Amino-4-phenyl-thiobutyric acid S-p-tolyl ester
  参考文献：
  名称：

  A New Approach to the Synthesis of .beta.-Hydroxy-.alpha.-amino Acids Using (Arylthio)nitrooxiranes

  摘要：

  2-(Arylthio)-2-nitrooxiranes, prepared by the nucleophilic epoxidation of 1-(arylthio)-1-nitroalkenes using anhydrous metal alkyl peroxides in tetrahydrofuran, react with aqueous ammonia to give alpha-amino thioesters in good yield, without significant formation of the primary amide by subsequent reaction of the thioester with ammonia. lit situ protection of the amino group is possible, leading to a range of protected derivatives. Diastereoselective epoxidation of 1-(arylthio)-1-nitroalkenes with an allylic, oxygen-substituted stereogenic center using metal alkyl peroxides is possible, and the sense of diastereoselectivity can be controlled simply by use of lithium or potassium as the counterion. Enhanced syn selectivity (15:1) in lithium tert-butyl peroxide mediated epoxidations can be achieved by using toluene as solvent. Use of potassium triphenylmethyl peroxide, rather than potassium tert-butyl peroxide, generally gives higher anti selectivity (12:1). Reactions of enantiomerically and diastereoisomerically pure 2-(arylthio)-2-nitrooxiranes with ammonia proceed stereospecifically with inversion of configuration, establishing a stereocontrolled route to beta-hydroxy-alpha-amino acids. Use of other nitrogen nucleophiles, for example amino acid esters, is also possible, leading to a stereospecific approach to a-amino dicarboxylic acids. Applications of this methodology, which constitutes a stereocontrolled Strecker reaction, to the synthesis of gamma-hydroxy threonine derivatives 19-22, polyoxamic acid (26), and the C-5 epimer of the sugar fragment of polyoxin C (27) are described.

  DOI：

  10.1021/jo00125a032
• 作为产物：
  描述：

  (p-tolylthio)nitromethane 在 potassium tert-butylate 、 lithium t-butyl peroxide 、 甲基磺酰氯 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 为溶剂， 生成 2-Nitro-3-phenethyl-2-p-tolylsulfanyl-oxirane
  参考文献：
  名称：

  A New Approach to the Synthesis of .beta.-Hydroxy-.alpha.-amino Acids Using (Arylthio)nitrooxiranes

  摘要：

  2-(Arylthio)-2-nitrooxiranes, prepared by the nucleophilic epoxidation of 1-(arylthio)-1-nitroalkenes using anhydrous metal alkyl peroxides in tetrahydrofuran, react with aqueous ammonia to give alpha-amino thioesters in good yield, without significant formation of the primary amide by subsequent reaction of the thioester with ammonia. lit situ protection of the amino group is possible, leading to a range of protected derivatives. Diastereoselective epoxidation of 1-(arylthio)-1-nitroalkenes with an allylic, oxygen-substituted stereogenic center using metal alkyl peroxides is possible, and the sense of diastereoselectivity can be controlled simply by use of lithium or potassium as the counterion. Enhanced syn selectivity (15:1) in lithium tert-butyl peroxide mediated epoxidations can be achieved by using toluene as solvent. Use of potassium triphenylmethyl peroxide, rather than potassium tert-butyl peroxide, generally gives higher anti selectivity (12:1). Reactions of enantiomerically and diastereoisomerically pure 2-(arylthio)-2-nitrooxiranes with ammonia proceed stereospecifically with inversion of configuration, establishing a stereocontrolled route to beta-hydroxy-alpha-amino acids. Use of other nitrogen nucleophiles, for example amino acid esters, is also possible, leading to a stereospecific approach to a-amino dicarboxylic acids. Applications of this methodology, which constitutes a stereocontrolled Strecker reaction, to the synthesis of gamma-hydroxy threonine derivatives 19-22, polyoxamic acid (26), and the C-5 epimer of the sugar fragment of polyoxin C (27) are described.

  DOI：

  10.1021/jo00125a032

文献信息

• A New Approach to the Synthesis of .beta.-Hydroxy-.alpha.-amino Acids Using (Arylthio)nitrooxiranes
  作者：Richard F. W. Jackson、Nicholas J. Palmer、Martin J. Wythes、William Clegg、Mark R. J. Elsegood

  DOI：10.1021/jo00125a032

  日期：1995.10

  2-(Arylthio)-2-nitrooxiranes, prepared by the nucleophilic epoxidation of 1-(arylthio)-1-nitroalkenes using anhydrous metal alkyl peroxides in tetrahydrofuran, react with aqueous ammonia to give alpha-amino thioesters in good yield, without significant formation of the primary amide by subsequent reaction of the thioester with ammonia. lit situ protection of the amino group is possible, leading to a range of protected derivatives. Diastereoselective epoxidation of 1-(arylthio)-1-nitroalkenes with an allylic, oxygen-substituted stereogenic center using metal alkyl peroxides is possible, and the sense of diastereoselectivity can be controlled simply by use of lithium or potassium as the counterion. Enhanced syn selectivity (15:1) in lithium tert-butyl peroxide mediated epoxidations can be achieved by using toluene as solvent. Use of potassium triphenylmethyl peroxide, rather than potassium tert-butyl peroxide, generally gives higher anti selectivity (12:1). Reactions of enantiomerically and diastereoisomerically pure 2-(arylthio)-2-nitrooxiranes with ammonia proceed stereospecifically with inversion of configuration, establishing a stereocontrolled route to beta-hydroxy-alpha-amino acids. Use of other nitrogen nucleophiles, for example amino acid esters, is also possible, leading to a stereospecific approach to a-amino dicarboxylic acids. Applications of this methodology, which constitutes a stereocontrolled Strecker reaction, to the synthesis of gamma-hydroxy threonine derivatives 19-22, polyoxamic acid (26), and the C-5 epimer of the sugar fragment of polyoxin C (27) are described.