(2R,3S)-3-Amino-1,2-epoxy-N-<(4-methylphenyl)sulfonyl>butane | 153710-23-7

• 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: (2R,3S)-3-Amino-1,2-epoxy-N-<(4-methylphenyl)sulfonyl>butane
• 英文别名: 4-methyl-N-[(1S)-1-[(2R)-oxiran-2-yl]ethyl]benzenesulfonamide
• CAS: 153710-23-7
• 化学式: C₁₁H₁₅NO₃S
• 分子量: 241.311
• InChiKey: CNNDHFPJCKVZSL-ONGXEEELSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  67.1
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  正丁基锂 、 (2R,3S)-3-Amino-1,2-epoxy-N-<(4-methylphenyl)sulfonyl>butane 在 1.) CuCN 作用下， 生成 (2S,3S)-2-Amino-3-hydroxy-N-<(4-methylphenyl)sulfonyl>octane
  参考文献：
  名称：

  Aza-Payne Rearrangement of Activated 2-Aziridinemethanols and 2,3-Epoxy Amines under Basic Conditions

  摘要：

  An aza-Payne rearrangement of activated 2-aziridinemethanols with t-BuOK, NaH, or KH at near 0 degrees C in common solvents such as THF, toluene, 1,2-dimethoxyethane, 1,4-dioxane, or a mixed solvent of THF-HMPA followed by quenching at -78 degrees C gives the corresponding epoxysulfonamides. Exposure of N-tosyl-(2S)-azetidinemethanol (36) and N-tosyl-(S)-prolinol (37) to NaH or KH in dichloromethane yielded only the respective dimeric compounds that resulted by joining 2 equiv of reactant through a methylene group. Reaction of N-tosyl-(2S,3S)-3-methyl-2-aziridinemethanol (9) and its (2R,3S)-isomer 23 with Gilman reagents (R(2)CuLi; R = Me and Bu) or ''higher order'' cuprates [R(2)Cu(CN)Li-2; R = Me and Bu] yielded the two expected aziridine ring-opening products. In sharp contrast, treatment of 9 and 23 with ''lower order'' cuprates afforded rearrangement-opened products. Thus, if the nucleophile is highly reactive, then the expected nucleophilic ring opening of the aziridine predominates. However, if the nucleophile is less reactive, then it becomes possible to cleave the resulting rearranged epoxide. Upon exposure of 2,3-epoxy amines to an equimolar mixture of t-BuOK-n-BuLi in a mixed solvent of THF and n-hexane at -78 degrees C, the equilibrium lies exclusively toward the hydroxy aziridine forming direction.

  DOI：

  10.1021/jo00112a028
• 作为产物：
  描述：

  (2S,3S)-2-hydroxymethyl-3-methyl-1-<(4-methylphenyl)sulfonyl>aziridine 在 sodium hydride 作用下， 以 四氢呋喃 、 六甲基磷酰三胺 为溶剂， 反应 18.0h， 以92%的产率得到(2R,3S)-3-Amino-1,2-epoxy-N-<(4-methylphenyl)sulfonyl>butane
  参考文献：
  名称：

  2-氮丙啶甲醇与“低级”甲基氰尿酸锂的空前重排反应

  摘要：

  可以通过使用吉尔曼试剂或低级氰尿酸酯在2-氮丙啶甲醇的开环反应中实现互补的选择性。在前一种情况下，吉尔曼试剂对底物1和2的通常攻击导致分别形成了预期的开环产物（3和4）和（7和8）。相反，将1和2都暴露于低级氰铜酸盐中却以前所未有的方式进行，大概是通过环氧化物D和G来生成意想不到的仲醇（11和12）作为主要产品。

  DOI：

  10.1016/s0040-4039(00)60142-9

文献信息

• Unprecedented rearrangement reaction of 2-aziridinemethanols with “lower order” lithium methylcyanocuprate
  作者：Toshiro Ibuka、Kazuo Nakai、Hiromu Habashita、Nobutaka Fujii、Fabrice Garrido、André Mann、Yukiyasu Chounan、Yoshinori Yamamoto

  DOI：10.1016/s0040-4039(00)60142-9

  日期：1993.11

  Complementary selectivity can be achieved in ring opening reactions of 2-aziridinemethanols by using either the Gilman reagent or lower order cyanocuprate. In the former case, the usual attack of the Gilman reagent to the substrates 1 and 2 results in the formation of the expected ring opening products (3 and 4) and (7 and 8), respectively. In contrast, exposure of both 1 and 2 to the lower order cyanocuprate

  可以通过使用吉尔曼试剂或低级氰尿酸酯在2-氮丙啶甲醇的开环反应中实现互补的选择性。在前一种情况下，吉尔曼试剂对底物1和2的通常攻击导致分别形成了预期的开环产物（3和4）和（7和8）。相反，将1和2都暴露于低级氰铜酸盐中却以前所未有的方式进行，大概是通过环氧化物D和G来生成意想不到的仲醇（11和12）作为主要产品。
• Aza-Payne Rearrangement of Activated 2-Aziridinemethanols and 2,3-Epoxy Amines under Basic Conditions
  作者：Toshiro Ibuka、Kazuo Nakai、Hiromu Habashita、Yuka Hotta、Akira Otaka、Hirokazu Tamamura、Nobutaka Fujii、Norio Mimura、Yoshihisa Miwa、Yukiyasu Chounan、Yoshinori Yamamoto

  DOI：10.1021/jo00112a028

  日期：1995.4

  An aza-Payne rearrangement of activated 2-aziridinemethanols with t-BuOK, NaH, or KH at near 0 degrees C in common solvents such as THF, toluene, 1,2-dimethoxyethane, 1,4-dioxane, or a mixed solvent of THF-HMPA followed by quenching at -78 degrees C gives the corresponding epoxysulfonamides. Exposure of N-tosyl-(2S)-azetidinemethanol (36) and N-tosyl-(S)-prolinol (37) to NaH or KH in dichloromethane yielded only the respective dimeric compounds that resulted by joining 2 equiv of reactant through a methylene group. Reaction of N-tosyl-(2S,3S)-3-methyl-2-aziridinemethanol (9) and its (2R,3S)-isomer 23 with Gilman reagents (R(2)CuLi; R = Me and Bu) or ''higher order'' cuprates [R(2)Cu(CN)Li-2; R = Me and Bu] yielded the two expected aziridine ring-opening products. In sharp contrast, treatment of 9 and 23 with ''lower order'' cuprates afforded rearrangement-opened products. Thus, if the nucleophile is highly reactive, then the expected nucleophilic ring opening of the aziridine predominates. However, if the nucleophile is less reactive, then it becomes possible to cleave the resulting rearranged epoxide. Upon exposure of 2,3-epoxy amines to an equimolar mixture of t-BuOK-n-BuLi in a mixed solvent of THF and n-hexane at -78 degrees C, the equilibrium lies exclusively toward the hydroxy aziridine forming direction.