(SS,7S)-3,3-pentamethylene-7-phenyl-8-(p-tolylsulfinyl)-1,2,3,5,6,7-hexahydro-2-oxa-5-indolizinone | 244104-74-3

• 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: (SS,7S)-3,3-pentamethylene-7-phenyl-8-(p-tolylsulfinyl)-1,2,3,5,6,7-hexahydro-2-oxa-5-indolizinone
• 英文别名: (S_S,7S)-3,3-pentamethylene-7-phenyl-8-(p-tolylsulfinyl)-1,2,3,5,6,7-hexahydro-2-oxa-5-indolizinone
• CAS: 244104-74-3
• 化学式: C₂₅H₂₇NO₃S
• 分子量: 421.56
• InChiKey: ABDLYHVUKXMFML-JRPXNJEYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.02
• 重原子数：
  30.0
• 可旋转键数：
  3.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  46.61
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  Methyl cinnamate 、 (SS,7S)-3,3-pentamethylene-7-phenyl-8-(p-tolylsulfinyl)-1,2,3,5,6,7-hexahydro-2-oxa-5-indolizinone 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 2.5h， 以83%的产率得到methyl (R)-3-((6'R,7'S)-5'-oxo-7'-phenyl-8'-((S)-p-tolylsulfinyl)-1',5',6',7'-tetrahydrospiro[cyclohexane-1,3'-oxazolo[3,4-a]pyridin]-6'-yl)-3-phenylpropanoate
  参考文献：
  名称：

  Total diastereoselectivity in the one-pot multistep reaction of (RS)-(+)-{[(4-methylphenyl)sulfinyl]methyl}-1-oxa-4-azaspiro[4.5]dec-3-ene and E-methyl cinnamate. An approach to (2S,4S,5R,6R)-2-(hydroxymethyl)-4,6-diphenyl-1-azabicycle[3.3.1]nonane

  摘要：

  The base-mediated reaction of enantiomerically pure alpha-sulfinylketimine (+)-1 with (E)-methyl cinnamate afforded (+)-5a in a one-pot procedure with complete diastereoselectivity. A sole diastereomer of the eight possible ones was isolated which revealed the stereocantrol of the chiral sulfinyl group in the construction of the three new stereogenic centres. The absolute configuration of stereocentres introduced in (+)-5a was assigned on the basis of H-1 NMR data and a single X-ray structure. (C) 2008 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2008.05.030
• 作为产物：
  描述：

  (1R,2S,5R,SS)-(-)-menthyl p-toluenesulfinate 在 正丁基锂 、 二异丙胺 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 2.0h， 生成 (SS,7S)-3,3-pentamethylene-7-phenyl-8-(p-tolylsulfinyl)-1,2,3,5,6,7-hexahydro-2-oxa-5-indolizinone
  参考文献：
  名称：

  Diastereoselective synthesis of 4-substituted 5-(p-tolylsulfinyl)-5,6-dehydropiperidin-2-ones. A new approach to methyl l-(2S,4S)-4-methyl-6-oxopipecolate

  摘要：

  The sulfoxide-mediated diastereoselective Michael reaction of homochiral alpha-sulfinylketimines 1a-d and beta-substituted ene esters 2a-d (Hua's reaction) was explored. Straight forward cyclization of the open-chain adducts take place under the reaction conditions to provide the 4-substituted 5-(p-tolylsulfinyl)-5,6-dehydropiperidin-2-ones 3 and 7-12, whose stereochemistry is formed in the prior step. Furthermore. the role of the metal ion of the aza-enolate reagents and the steric demands of the O-alkyl ester group have been examined. It seems that the anti-diastereoselectivity depends on metal chelation by the oxygen of the ester as well as the oxygen of the sulfinyl group and the nitrogen in the aza-enolate ((Z)-configuration). In addition, the synthesis of methyl L-(2S,4S)-4-methyl-6-oxopipecolate has been achieved from the suitably functionalized 2-sulfinylketimine 1a (five steps; overall yield: 53-65%). (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(01)00553-5

文献信息

• Sulfoxide-mediated diastereoselective Michael additions. New enantioselective synthesis of C-4 substituted 2-pyroaminoadipic acids
  作者：Hassan Acherki、Carlos Alvarez-Ibarra、Alicia Barrasa、Alfonso de Dios

  DOI：10.1016/s0040-4039(99)01047-3

  日期：1999.7

  Diastereoselective reactions of suitably functionalized homochiral beta-iminosulfoxides with Michael accepters provide a new and efficient route for the asymmetric synthesis of C-4 substituted 2-pyroaminoadipates. Extension of the scope of the sulfoxide-mediated aza-enolate conjugate addition (Hua's reaction) has also been explored. (C) 1999 Elsevier Science Ltd. All rights reserved.
• Diastereoselective synthesis of 4-substituted 5-(p-tolylsulfinyl)-5,6-dehydropiperidin-2-ones. A new approach to methyl l-(2S,4S)-4-methyl-6-oxopipecolate
  作者：Hassan Acherki、Carlos Alvarez-Ibarra、Alfonso de Dios、Marta Gutiérrez、Marı́a L. Quiroga

  DOI：10.1016/s0957-4166(01)00553-5

  日期：2001.12

  The sulfoxide-mediated diastereoselective Michael reaction of homochiral alpha-sulfinylketimines 1a-d and beta-substituted ene esters 2a-d (Hua's reaction) was explored. Straight forward cyclization of the open-chain adducts take place under the reaction conditions to provide the 4-substituted 5-(p-tolylsulfinyl)-5,6-dehydropiperidin-2-ones 3 and 7-12, whose stereochemistry is formed in the prior step. Furthermore. the role of the metal ion of the aza-enolate reagents and the steric demands of the O-alkyl ester group have been examined. It seems that the anti-diastereoselectivity depends on metal chelation by the oxygen of the ester as well as the oxygen of the sulfinyl group and the nitrogen in the aza-enolate ((Z)-configuration). In addition, the synthesis of methyl L-(2S,4S)-4-methyl-6-oxopipecolate has been achieved from the suitably functionalized 2-sulfinylketimine 1a (five steps; overall yield: 53-65%). (C) 2002 Elsevier Science Ltd. All rights reserved.
• Total diastereoselectivity in the one-pot multistep reaction of (RS)-(+)-{[(4-methylphenyl)sulfinyl]methyl}-1-oxa-4-azaspiro[4.5]dec-3-ene and E-methyl cinnamate. An approach to (2S,4S,5R,6R)-2-(hydroxymethyl)-4,6-diphenyl-1-azabicycle[3.3.1]nonane
  作者：Carlos Alvarez-Ibarra、Juan F. Collados Luján、Maria L. Quiroga-Feijóo、Gonzalo Rodríguez

  DOI：10.1016/j.tetasy.2008.05.030

  日期：2008.6

  The base-mediated reaction of enantiomerically pure alpha-sulfinylketimine (+)-1 with (E)-methyl cinnamate afforded (+)-5a in a one-pot procedure with complete diastereoselectivity. A sole diastereomer of the eight possible ones was isolated which revealed the stereocantrol of the chiral sulfinyl group in the construction of the three new stereogenic centres. The absolute configuration of stereocentres introduced in (+)-5a was assigned on the basis of H-1 NMR data and a single X-ray structure. (C) 2008 Elsevier Ltd. All rights reserved.