methyl (E)-3-[(2R,3S)-3-methyl-1-(4-methylphenyl)sulfonylaziridin-2-yl]prop-2-enoate | 158411-81-5

• 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: methyl (E)-3-[(2R,3S)-3-methyl-1-(4-methylphenyl)sulfonylaziridin-2-yl]prop-2-enoate
• CAS: 158411-81-5
• 化学式: C₁₄H₁₇NO₄S
• 分子量: 295.359
• InChiKey: CCBZBLUNHZKKAA-XHSPCEQESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  20
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  71.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  methyl (E)-3-[(2R,3S)-3-methyl-1-(4-methylphenyl)sulfonylaziridin-2-yl]prop-2-enoate 在 盐酸 作用下， 以 1,4-二氧六环 为溶剂， 反应 0.5h， 以92%的产率得到methyl (2E,4S,5S)-4-chloro-5-(4-methylphenylsulfonylamino)hex-2-enoate
  参考文献：
  名称：

  Stereoselective synthesis of a set of two functionalized (E)-alkene dipeptide isosteres of L-amino acid-L-Glu and L-amino acid-D-Glu

  摘要：

  N-arylsulfonyl-γ,δ-cis- or -trans-γ,δ-epimino (E)-α,β-烯酸盐用 HCl-1,4- 二氧六环处理后，可得到具有区域和立体选择性的开环产物--δ-氨基 γ-氯-α,β-烯酸盐。这种开环反应为使用有机锌铜试剂从单一底物γ,δ-表亚胺 (E)-α,β-烯酸盐立体选择性合成一组非对映异构体 (L-Xaa, L-Glu) 型和 (L-Xaa, D-Glu) 型 (E)- 烯二肽异构体 (EADIs) 提供了一种有用的方法。

  DOI：

  10.1039/b103833h
• 作为产物：
  描述：

  (2S,3S)-2-hydroxymethyl-3-methyl-1-<(4-methylphenyl)sulfonyl>aziridine 在 戴斯-马丁氧化剂 作用下， 以 二氯甲烷 为溶剂， 反应 4.0h， 生成 methyl (E)-3-[(2R,3S)-3-methyl-1-(4-methylphenyl)sulfonylaziridin-2-yl]prop-2-enoate
  参考文献：
  名称：

  SN2'-Reactions of Peptide Aziridines. A Cuprate-Based Approach to (E)-Alkene Isosteres

  摘要：

  Alkenylaziridines were prepared from allylic alcohols via Sharpless epoxidation; oxirane to aziridine conversion under modified Staudinger conditions, and Wittig chain extension. Alternatively, beta-hydroxy alpha-amino acids such as threonine can serve as readily available precursors. The corresponding N-acyl, -peptidyl-, -carbamoyl-, and -sulfonylaziridines underwent a high-yielding anti-S(N)2' alkylation with organocopper/BF3 complex to give (E)-alkene peptide isosteres in 62 to >98% de. The stereoselectivity of the addition process was studied by H-1 and F-19 NMR as well as chemical degradation. Alkene isosteres are important nonhydrolyzable and rigidified analogs of peptide bonds in biologically active peptides. This new methodology considerably facilitates the synthesis and the study of these peptide mimetics, since alkenylaziridines are readily prepared and side-chain modification is simplified by the wide range of functionalized organocopper reagents that are available.

  DOI：

  10.1021/jo00096a033

文献信息

• Versatile use of acid-catalyzed ring-opening of β-aziridinyl-α,β-enoates to stereoselective synthesis of peptidomimetics
  作者：Hirokazu Tamamura、Tomohiro Tanaka、Hiroshi Tsutsumi、Koji Nemoto、Satoko Mizokami、Nami Ohashi、Shinya Oishi、Nobutaka Fujii

  DOI：10.1016/j.tet.2007.06.029

  日期：2007.9

  β-unsaturated esters with alcohols, thiols or weak acids such as AcOH in the presence of catalytic amount of Lewis acids affords regio- and stereoselectively ring-opened products, such as δ-aminated γ-alkoxy-(alkylthio or acetoxy)-α,β-enoates. In addition, the regio- and stereoselective ring-opening reactions can be performed on solid supports and applied to stereoselective synthesis of (E)-alkene

  在催化量的路易斯酸存在下，用醇，硫醇或弱酸（如AcOH）处理带有α，β-不饱和酯的N-芳基磺酰基氮丙啶，可提供区域选择性和立体选择性的开环产物，例如δ胺化的γ-烷氧基- （烷硫基或乙酰氧基）-α，β-烯酸酯。另外，可以在固体载体上进行区域选择性和立体选择性的开环反应，并将其用于（E）-烯烃二肽等排体的立体选择性合成。
• Highly Stereoselective Samarium(II) Iodide-Mediated Aldol Reactions of Acylaziridines with Aldehydes
  作者：Yasuyuki Ogawa、Kiichi Kuroda、Teruaki Mukaiyama

  DOI：10.1246/bcsj.78.1309

  日期：2005.7

  The samarium(II) iodide-mediated stereoselective aldol reactions of acylaziridines with aldehydes are described. β-Amino-β'-hydroxy ketones were synthesized in high yields by the aldol reaction of aldehydes with samarium enolates generated by aziridine-fragmentation of aziridinyl ketones with two moles of samarium(II) iodide. By the choice of an appropriate nitrogen protecting group, depending on the

  描述了碘化钐 (II) 介导的酰基氮丙啶与醛的立体选择性羟醛反应。β-氨基-β'-羟基酮是通过醛与钐烯醇的羟醛反应以高产率合成的，钐烯醇化物是通过用两摩尔碘化钐（II）对氮丙啶基酮进行氮丙啶裂解而产生的。通过选择合适的氮保护基团，根据氮丙啶酮的 C-3 位取代基，在四种可能的非对映异构体中非对映选择性地获得抗、抗-β-氨基-无-β'-羟基酮。此外，当使用手性氮丙啶酮时，通过这种羟醛反应成功地获得了对映体纯的抗、抗-β-氨基-β'-羟基酮。此外，δ-氨基-β'-羟基-β，通过使用两摩尔碘化钐 (II) 的 γ,δ-氮丙啶基-α,β-不饱和酯的氮丙啶断裂和烯烃迁移产生的醛与烯醇钐的羟醛反应，也可以高产率合成 γ-不饱和酯. 该醛醇反应以完全的α-区域选择性进行并选择性地形成（E）-烯烃。通过在γ,δ-氮丙啶基-α,β-不饱和羰基体系中引入手性恶唑烷-2-one助剂，该反应成功地扩展到不对称反应
• A thermodynamic preference of chiral cis-γ,δ-epimino-(E)-α,β-unsaturated esters over other stereoisomers: Synthetically useful Pd(0)-catalyzed equilibrated reactions of aziridines bearing an α,β-unsaturated ester group
  作者：Toshiro Ibuka、Masako Akaji、Norio Mimura、Hiromu Habashita、Kazuo Nakai、Hirokazu Tamamura、Nobutaka Fujii、Yoshinori Yamamoto

  DOI：10.1016/0040-4039(96)00403-0

  日期：1996.4

  A practical synthesis of chiral N-arylsulfonyl-cis-γ,δ-epimino-(E)-α,β-enoates, key intermediates for the synthesis of (E)-alkene dipeptide isosteres via Pd(0)-catalyzed equilibrated reactions, has been successfully achieved by exposing N-arylsulfonyl-γ,δ-epimino-α,β-unsaturated esters to a catalytic amount of Pd(PPh3)4 in THF at 0 ∼ 20 °C.

  手性的实用合成Ñ -arylsulfonyl-顺- γ，δ -epimino-（ë） - α，β -enoates，对（合成关键中间体ë） -烯烃电子等排体的二肽通过钯（0）催化的平衡反应，通过将N-芳基磺酰基-γ，δ-表-氨基-α，β-不饱和酯暴露于催化量的Pd（PPh 3）4在THF中的温度为0到20°C，可以成功地实现这一目的。
• Fujii, Nobutaka; Nakai, Kazuo; Tamamura, Hirokazu, Journal of the Chemical Society. Perkin transactions I, 1995, # 11, p. 1359 - 1372
  作者：Fujii, Nobutaka、Nakai, Kazuo、Tamamura, Hirokazu、Otaka, Akira、Mimura, Norio、et al.

  DOI：——

  日期：——
• Palladium-catalyzed reductive ring opening with formic acid of aziridines bearing an α,β-unsaturated ester group
  作者：Hiroaki Ohno、Norio Mimura、Akira Otaka、Hirokazu Tamamura、Nobutaka Fujii、Toshiro Ibuka、Isao Shimizu、Akiharu Satake、Yoshinori Yamamoto

  DOI：10.1016/s0040-4020(97)00817-x

  日期：1997.9

  The palladium-catalyzed reduction of various N-arenesulfonylaziridines bearing alpha,beta-unsaturated ester groups with formic acid and the stereochemistry of the reaction products have been investigated in detail. In all cases examined, (Z)-alpha,beta-enoates, (E)-alpha,beta-enoates, and (E)-beta,gamma-enoates bearing amino functionality at the delta-position were obtained. The formation of these three reduction products was taken as an indication that palladium-catalyzed isomerization occurs prior to the reduction step. (C) 1997 Elsevier Science Ltd.