(+)-(E,S_S,2S,3R)-5-[N-methyl-S-phenylsulfonimidoyl]-3-methyl-2-[(2-methylprop-2-ylsulfonyl)-prop-2-ynylamino]-pent-4-enoic acid ethyl ester | 616234-10-7

• 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: (+)-(E,S_S,2S,3R)-5-[N-methyl-S-phenylsulfonimidoyl]-3-methyl-2-[(2-methylprop-2-ylsulfonyl)-prop-2-ynylamino]-pent-4-enoic acid ethyl ester
• 英文别名: ethyl (E,2S,3R)-2-[tert-butylsulfonyl(prop-2-ynyl)amino]-3-methyl-5-(N-methyl-S-phenylsulfonimidoyl)pent-4-enoate
• CAS: 616234-10-7
• 化学式: C₂₂H₃₂N₂O₅S₂
• 分子量: 468.638
• InChiKey: WQJJWSXYBDHUBY-YQEZQSROSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  31
• 可旋转键数：
  11
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  110
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  (+)-(E,S_S,2S,3R)-5-[N-methyl-S-phenylsulfonimidoyl]-3-methyl-2-[(2-methylprop-2-ylsulfonyl)-prop-2-ynylamino]-pent-4-enoic acid ethyl ester 、 alkaline earth salt of/the/ methylsulfuric acid 在 N-甲基吲哚酮 作用下， 以 四氢呋喃 为溶剂， 反应 0.5h， 以49%的产率得到(-)-(3S,4R,4aR)-2,3,4,4a,5,6-hexahydro-4-methyl-2-(2-methylprop-2-yl-sulfonyl)-6-oxo-1H-cyclopenta[c]pyridine-3-carboxylic acid ethyl ester
  参考文献：
  名称：

  Asymmetric Synthesis of Fused Bicyclic α-Amino Acids Having a Hexahydro-cyclopenta[c]pyridine Skeleton via Intramolecular Pauson−Khand Reaction of 1-Sulfonimidoyl-Substituted 5-Azaoct-1-en-7-ynes

  摘要：

  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.

  DOI：

  10.1021/jo030171x
• 作为产物：
  描述：

  (+)-(E,S)-N-methyl-S-(2-butenyl)-S-phenylsulfoximine 在 正丁基锂 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 反应 0.25h， 生成 (+)-(E,S_S,2S,3R)-5-[N-methyl-S-phenylsulfonimidoyl]-3-methyl-2-[(2-methylprop-2-ylsulfonyl)-prop-2-ynylamino]-pent-4-enoic acid ethyl ester 、 alkaline earth salt of/the/ methylsulfuric acid
  参考文献：
  名称：

  Asymmetric Synthesis of Fused Bicyclic α-Amino Acids Having a Hexahydro-cyclopenta[c]pyridine Skeleton via Intramolecular Pauson−Khand Reaction of 1-Sulfonimidoyl-Substituted 5-Azaoct-1-en-7-ynes

  摘要：

  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.

  DOI：

  10.1021/jo030171x

文献信息

• 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.