ethyl (2S,3R,E)-3-cyclohexyl-2-((1,1-dimethylethyl)sulfonamido)-5-(N-methylphenylsulfonimidoyl)pent-4-enoate | 445010-35-5

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: ethyl (2S,3R,E)-3-cyclohexyl-2-((1,1-dimethylethyl)sulfonamido)-5-(N-methylphenylsulfonimidoyl)pent-4-enoate
• CAS: 445010-35-5
• 化学式: C₂₄H₃₈N₂O₅S₂
• 分子量: 498.708
• InChiKey: KZJIWKLJEJOVRZ-MSMNTQNBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  33.0
• 可旋转键数：
  9.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  101.9
• 氢给体数：
  1.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  ethyl (2S,3R,E)-3-cyclohexyl-2-((1,1-dimethylethyl)sulfonamido)-5-(N-methylphenylsulfonimidoyl)pent-4-enoate 在 potassium fluoride 作用下， 以 二氯甲烷 为溶剂， 反应 4.0h， 生成 (-)-(S)-3-cyclohexyl-1-(tert-butylsulfonyl)-2,5-dihydro-1H-pyrrole-2-carboxylic acid ethyl ester
  参考文献：
  名称：

  由手性亚磺酰亚胺取代的烯丙基钛（IV）配合物不对称合成3-取代的不饱和脯氨酸

  摘要：

  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。

  DOI：

  10.1016/j.tetlet.2004.09.062
• 作为产物：
  描述：

  环己基乙醛 在 正丁基锂 、 1,2-diazabicyclo[5.4.0]undec-7-ene 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 四氢呋喃 、 正己烷 、 乙腈 为溶剂， 反应 9.0h， 生成 ethyl (2S,3R,E)-3-cyclohexyl-2-((1,1-dimethylethyl)sulfonamido)-5-(N-methylphenylsulfonimidoyl)pent-4-enoate
  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

文献信息

• Asymmetric aziridination with chiral allyl aminosulfoxonium ylides: synthesis of alkenyl aziridine carboxylates and palladium-catalyzed E,trans/E,cis-isomerization of an alkenyl aziridine
  作者：Vijaya Bhaskara Reddy Iska、Hans-Joachim Gais、Shashi Kant Tiwari、Gadamsetti Surendra Babu、Adeline Adrien

  DOI：10.1016/j.tetlet.2007.07.216

  日期：2007.10

  Chiral cyclic and acyclic allyl aminosulfoxonium ylides have been generated from aminosulfoxonium-substituted β,γ-unsaturated α-amino acids (method A) and 1-alkenyl aminosulfoxonium salts (method B) upon treatment with DBU. Their application to the asymmetric aziridination of N-tert-butyl-sulfonyl imino ester, generated either in situ (method A) or externally added (method B), gave the corresponding

  在用DBU处理后，由氨基s取代的β，γ-不饱和α-氨基酸（方法A）和1-烯基氨基s生成的盐（方法B）已生成手性环状和无环烯丙基氨基ulf氧化物。其应用到的不对称氮杂环丙烷Ñ -叔丁基-磺酰亚氨基酯，原位（方法A）或外部添加（方法B）或者生成，得到相应的链烯基的氮丙啶羧酸盐与中到高非对映选择性和对映选择性。描述了E，反式构型的烯基氮丙啶甲醇衍生物到其E-顺式异构体的高度立体选择性Pd（0）-催化的异构化，其继续保持双键构型。
• 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.