(tert-butylsulfonylimino)acetic acid ethyl ester | 445010-18-4

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: (tert-butylsulfonylimino)acetic acid ethyl ester
• 英文别名: (2-methyl-propane-2-sulfonylimino) acetic acid ethyl ester；ethyl (2E)-2-tert-butylsulfonyliminoacetate
• CAS: 445010-18-4
• 化学式: C₈H₁₅NO₄S
• 分子量: 221.277
• InChiKey: ZVVWTQJQWLCNOG-RMKNXTFCSA-N

物化性质

• 沸点：
  95-105 °C(Press: 0.2 Torr)
• 密度：
  1.15±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  81.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (tert-butylsulfonylimino)acetic acid ethyl ester 在 正丁基锂 、 trimethoxonium tetrafluoroborate 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 11.25h， 生成 (-)-(S)-3-isopropyl-1-(tert-butylsulfonyl)-2,5-dihydro-1H-pyrrole-2-carboxylic acid ethyl ester
  参考文献：
  名称：

  Functionalized Chiral Vinyl Aminosulfoxonium Salts:  Asymmetric Synthesis and Application to the Synthesis of Enantiopure Unsaturated Prolines, β,γ-Dehydro Amino Acids, and Cyclopentanoid Keto Aminosulfoxonium Ylides

  摘要：

  Methylation of the enantiopure functionalized vinyl sulfoximines 5a-e and 14a-d followed by a F-ion or DBU-mediated isomerization of the vinyl aminosulfoxonium salts 7a-e and 15a-d, respectively, gave the allyl aminosulfoxonium salts 10a-e and 17a-d, respectively. A concomitant intramolecular substitution of the aminosulfoxonium group of 10a-e and 17a-d by the amino group afforded the unsaturated prolines 8a-e and 18a-d, respectively. The starting vinyl sulfoximines are accessible through a highly selective and stereo-complementary aminoalkylation of the corresponding sulfonimidoyl-substituted mono- and bis( allyl) titanium complexes with the imino ester 4. The vinyl aminosulfoxonium salts 34, 7a-d, and E-15c experienced upon treatment with the Cl- ion a migratory substitution with formation of the delta-chloro-beta,gamma-dehydro amino acids 36, E/Z-37a-d, and 38, respectively. A migratory substitution of the hydroxy-substituted vinyl aminosulfoxonium salts 46a and 46b furnished the delta-chloro allyl alcohols E/Z-48a and E-48b, respectively. A facile one-pot conversion of the vinyl sulfoximines 31b, 5c and 45a to the allyl chlorides 36, E/Z-37c and E/Z-48a, respectively, was achieved upon treatment with a chloroformiate. A tandem cyclization of the vinyl aminosulfoxonium salts 7b, Al-7b and 57 with LiN( H) tBu yielded the cyclopentanoid keto aminosulfoxonium ylides 54, Al-54, 59, 60 and 61, respectively. The structure of the tricyclic keto aminosulfoxonium ylide Al-54 has been determined by X-ray crystal structure analysis. Ab initio calculations and a NBO analysis of the tricyclic keto aminosulfoxonium ylide XXIII show a polar structure stabilized by electrostatic interactions between the ylidic C atom and both the carbonyl C atom and the S atom.

  DOI：

  10.1021/ja061152i
• 作为产物：
  描述：

  乙醛酸乙酯 、 叔丁基磺酰胺 在 氯化亚砜 作用下， 以 甲苯 为溶剂， 反应 82.0h， 以63%的产率得到(tert-butylsulfonylimino)acetic acid ethyl ester
  参考文献：
  名称：

  (2-甲基-丙烷-2-磺酰基亚氨基)乙酸乙酯的制备

  摘要：

  描述了由叔丁基磺酰胺、亚硫酰氯和乙醛酸乙酯合成(2-甲基-丙烷-2-磺酰基亚氨基)乙酸乙酯。N-叔丁基磺酰基亚氨基酯在烯丙基化反应中用作相应的N-甲苯磺酰基亚氨基酯的替代物。

  DOI：

  10.1055/s-2004-815925

文献信息

• Asymmetric synthesis of 3-substituted unsaturated prolines from chiral sulfoximine substituted allyl titanium(IV) complexes
  作者：Shashi Kant Tiwari、Andreas Schneider、Stefan Koep、Hans-Joachim Gais

  DOI：10.1016/j.tetlet.2004.09.062

  日期：2004.11

  ester 3. Activation of sulfoximines 4a–e and 11a–c through methylation of the sulfoximine group followed by a KF mediated isomerization of the vinyl aminosulfoxonium salts 5a–e and 12a–c, respectively, to the corresponding allyl aminosulfoxonium salt 6a–e and 13a–c, respectively, and a subsequent intramolecular nucleophilic substitution of the allylic aminosulfoxonium group afforded the enantio- and diastereomerically

  3-取代的Δ的不对称合成3,4-不饱和脯氨酸7A - ë和3-取代的4-亚甲基脯氨酸14A - Ç从相应的起始γ，δ不饱和α氨基酸4A - ë和11A - Ç，分别描述。氨基酸衍生物4a – e和11a – d是通过相应的磺胺亚胺取代的烯丙基钛（IV）配合物2a – e和10a – d的氨基烷基化获得的分别与Ñ -叔-butylsulfonyl亚氨酸酯3。通过亚砜亚胺基团的甲基化活化亚砜亚胺4a – e和11a – c，然后通过KF介导的乙烯基氨基亚砜氧鎓盐5a – e和12a – c分别异构化为相应的烯丙基氨基亚砜氧鎓盐6a – e和13a – c分别地，以及随后的烯丙基氨基亚砜基团的分子内亲核取代以中等至高收率提供了对映体和非对映体纯的脯氨酸衍生物。
• Highly Selective Addition of Chiral, Sulfonimidoyl Substituted Bis(allyl)titanium Complexes to <i>N</i>-Sulfonyl α-Imino Esters:  Asymmetric Synthesis of γ,δ-Unsaturated α-Amino Acids Bearing a Chiral, Electron-Withdrawing Nucleofuge at the δ-Position
  作者：Marcel Schleusner、Hans-Joachim Gais、Stefan Koep、Gerhard Raabe

  DOI：10.1021/ja0201799

  日期：2002.7.1

  nucleofuge at the δ-position and a cyclohexyl, an isopropyl, a phenyl, and a methyl group at the β-position. Addition of the cyclic bis(allyl)titanium complex 14 to N-Bus α-imino ester 9c afforded with similar high regio- and diastereoselectivities the (E)- and (Z)-configured amino acid derivatives (E)-8 and (Z)-8. Reaction of complexes 5a−d with α-imino esters 9a−c in the presence of Ti(OiPr)4 occurs

  将在 Cα-原子方面构型不稳定的手性磺酰亚胺酰基取代的双（烯丙基）钛配合物 5a-d 选择性加成到 N-甲苯磺酰基（Ts）-、N-2-三甲基甲硅烷基乙磺酰基（SES）-和N-叔丁基磺酰基 (Bus) α-亚氨基酯 (9a-c) 在 Ti(OiPr)4 和 ClTi(OiPr)3 存在下具有高区域选择性和非对映选择性，产生了 (syn, E)-配置β-烷基-γ,δ-不饱和α-氨基酸衍生物2a-g，在δ-位带有手性吸电子核，在β-带有环己基、异丙基、苯基和甲基位置。将环状双（烯丙基）钛络合物 14 添加到 N-Bus α-亚氨基酯 9c 中，以类似的高区域选择性和非对映选择性提供（E）-和（Z）-构型的氨基酸衍生物（E）-8 和（Z） )-8。
• Asymmetric Synthesis of Unsaturated, Fused Bicyclic Proline Analogues through Amino Alkylation of Cyclic Bis(allylsulfoximine)titanium Complexes and Migratory Cyclization of δ-Amino Alkenyl Aminosulfoxonium Salts
  作者：Stefan Koep、Hans-Joachim Gais、Gerhard Raabe

  DOI：10.1021/ja030324y

  日期：2003.10.1

  syn)-configured, delta-sulfoximine substituted, cyclic gamma,delta-unsaturated alpha-amino acid esters with high regio- and diastereoselectivities in good yields. Activation of the N-methyl sulfoximine group of these amino acid derivatives through methylation with Me(3)OBF(4) afforded in nearly quantitative yields the corresponding (dimethylamino)sulfoxonium salts. A novel migratory cyclization of these

  描述了由环状双（烯丙基亚砜亚胺）钛配合物和 N-叔丁基磺酰基亚氨基乙酯不对称合成新的 Delta(3a,4)-不饱和稠合双环脯氨酸类似物。用亚氨基酯处理对映体纯的五元、六元、七元和八元环状双（烯丙基亚砜亚胺）钛络合物，得到相应的 (E,syn)-和 (Z,syn)-构型的混合物，δ -亚砜亚胺取代的环状γ，δ-不饱和α-氨基酸酯，具有高产率和非对映选择性。这些氨基酸衍生物的 N-甲基亚砜亚胺基团通过甲基化与 Me(3)OBF(4) 活化，以几乎定量的方式提供相应的 (二甲氨基) 锍盐。这些盐与 DBU 的新型迁移环化通过异构化为相应的烯丙基（二甲氨基）锍盐和（二甲氨基）锍基团的分子内取代得到对映和非对映异构纯、双环、N-叔丁基磺酰基保护的脯氨酸类似物具有六元和八元不饱和碳环。烯基（二甲氨基）锍盐的环化与双键的构型无关。作为进一步的反应产物，以良好的收率获得≥99％ee的N，N-二甲基苯基亚
• Asymmetric Synthesis of Fused Bicyclic α-Amino Acids Having a Hexahydro-cyclopenta[<i>c</i>]pyridine Skeleton via Intramolecular Pauson−Khand Reaction of 1-Sulfonimidoyl-Substituted 5-Azaoct-1-en-7-ynes
  作者：Markus Günter、Hans-Joachim Gais

  DOI：10.1021/jo030171x

  日期：2003.10.1

  An asymmetric synthesis of fused bicyclic amino acids having a hexahydro-cyclopenta[c]pyridine skeleton and carrying besides an enone structural element a substituent at the beta-position is described. The key steps of the synthesis are a highly selective allylation of N-tert-butylsulfonyl imino ester with bis(allylsulfoximine)titanium complexes and a highly diastereoselective Pauson-Khand cycloaddition of sulfonimidoyl-substituted gamma,delta-unsaturated alpha-amino acid esters carrying a substituent at the beta-position and a propargyl group at the N-atom. The cyclization is accompanied by a reductive cleavage of the sulfoximine group of the primary cyclization product. Surprisingly, the removal of the sulfoximine group proceeds with inversion of the configuration at the S-atom and gives N-methyl-phenylsulfinamide with greater than or equal to98% ee. Deprotection of the bicyclic N-tert-butylsulfonyl-protected amino acid ester was accomplished through treatment with CF3SO3H under anhydrous conditions. The enantio- and diastereomerically pure sulfoximine-substituted gamma,delta-unsaturated alpha-amino acid esters used as starting material were obtained through a highly regio- and diastereoselective allylation of N-tert-butylsulfonyl imino ester with acyclic bis(allylsulfoximine)titanium complexes, described previously.
• Preparation of (2-Methyl-propane-2-sulfonylimino) Acetic Acid Ethyl Ester
  作者：Hans-Joachim Gais、Marcel Schleusner、Stefan Koep、Markus Günter、Shashi K. Tiwari

  DOI：10.1055/s-2004-815925

  日期：——

  Synthesis of (2-methyl-propane-2-sulfonylimino) acetic acid ethyl ester from tert-butylsulfonamide, thionyl chloride and ethyl glyoxylate is described. The N-tert-butylsulfonyl imino ester has served as a substitute of the corresponding N-toluenesulfonyl imino ester in allylation reactions.

  描述了由叔丁基磺酰胺、亚硫酰氯和乙醛酸乙酯合成(2-甲基-丙烷-2-磺酰基亚氨基)乙酸乙酯。N-叔丁基磺酰基亚氨基酯在烯丙基化反应中用作相应的N-甲苯磺酰基亚氨基酯的替代物。