(Z)-(4S)-2,2-dimethoxy-4-<2'-<4''-(methylphenyl)thio>-2'-nitroethenyl>-1,3-dioxolane | 150640-12-3

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: (Z)-(4S)-2,2-dimethoxy-4-<2'-<4''-(methylphenyl)thio>-2'-nitroethenyl>-1,3-dioxolane
• 英文别名: (4S)-2,2-dimethyl-4-[(Z)-2-(4-methylphenyl)sulfanyl-2-nitroethenyl]-1,3-dioxolane
• CAS: 150640-12-3
• 化学式: C₁₄H₁₇NO₄S
• 分子量: 295.359
• InChiKey: LXCZFYNPNGEVTA-LFTLCWSBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.36
• 重原子数：
  20.0
• 可旋转键数：
  4.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  61.6
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  (Z)-(4S)-2,2-dimethoxy-4-<2'-<4''-(methylphenyl)thio>-2'-nitroethenyl>-1,3-dioxolane 在 叔丁基过氧化氢 、 ammonium hydroxide 、 正丁基锂 作用下， 以 正己烷 、 二氯甲烷 、 甲苯 为溶剂， 反应 3.0h， 生成 S-(4''-methylphenyl) (2'R,4S)-2'-<(tert-butyloxycarbonyl)amino>-2'-(2,2-dimethyl-1,3-dioxolan-4-yl)ethanethioate
  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 、 (R)-(+)-2,2-二甲基-1,3-二氧戊环-4-甲醛 在 potassium tert-butylate 、 甲基磺酰氯 、 三乙胺 作用下， 生成 (Z)-(4S)-2,2-dimethoxy-4-<2'-<4''-(methylphenyl)thio>-2'-nitroethenyl>-1,3-dioxolane
  参考文献：
  名称：

  Control of diastereoselectivity in the nucleophilic epoxidation of 1-arylthro-1-nitroalkenes: synthesis of diastereoisomerically pure γ-hydroxy threonine derivatives

  摘要：

  由D-异亚丙基甘油醛衍生的1-硝基-1-（对甲苯硫基）烯烃1与过氧叔丁醇锂反应，以中等选择性生成顺式环氧乙烷2，而与过氧叔丁醇钾反应则主要生成反式非对映异构体3；环氧乙烷2和3与包括氨在内的胺类反应，得到纯非对映异构的α-氨基硫酯，无任何立体异构污染。

  DOI：

  10.1039/c39930000889

文献信息

• Control of diastereoselectivity in the nucleophilic epoxidation of 1-arylthro-1-nitroalkenes: synthesis of diastereoisomerically pure γ-hydroxy threonine derivatives
  作者：Richard F. W. Jackson、Joanna M. Kirk、Nicholas J. Palmer、David Waterson、Martin J. Wythes

  DOI：10.1039/c39930000889

  日期：——

  Epoxidation of the 1-nitro-1-(p-tolylthio)alkene 1 derived from D-isopropylideneglyceraldehyde with lithium tert-butyl peroxide affords the syn epoxide 2 with moderate selectivity, whereas epoxidation with potassium tert-butyl peroxide affords the anti diastereoisomer 3 preferentially; treatment of each of the epoxides 2 and 3 with amines, including ammonia, gives diastereoisomerically pure α-amino thioesters with no trace of stereoisomeric contamination.

  由D-异亚丙基甘油醛衍生的1-硝基-1-（对甲苯硫基）烯烃1与过氧叔丁醇锂反应，以中等选择性生成顺式环氧乙烷2，而与过氧叔丁醇钾反应则主要生成反式非对映异构体3；环氧乙烷2和3与包括氨在内的胺类反应，得到纯非对映异构的α-氨基硫酯，无任何立体异构污染。
• 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.