(4R,5S)-4-(2,2-dimethoxyethyl)-5-nitrocyclohex-1-ene

• 分子结构分类: 有机化合物 - 有机1,3-偶极化合物 - 烯丙基型1,3-偶极有机化合物
• 英文名称: (4R,5S)-4-(2,2-dimethoxyethyl)-5-nitrocyclohex-1-ene
• 英文别名: trans-4-(2,2-Dimethoxyethyl)-5-nitro-1-cyclohexene；(4R,5S)-4-(2,2-dimethoxyethyl)-5-nitrocyclohexene
• 化学式: C₁₀H₁₇NO₄
• 分子量: 215.249
• InChiKey: CDJXDHFXKIOZSR-BDAKNGLRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  64.3
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (4R,5S)-4-(2,2-dimethoxyethyl)-5-nitrocyclohex-1-ene 在 palladium 10% on activated carbon 、 氢气 作用下， 以 氘代甲醇-d 为溶剂， 反应 24.0h， 以80%的产率得到
  参考文献：
  名称：

  Organocatalytic Michael Addition/Intramolecular Julia–Kocienski Olefination for the Preparation of Nitrocyclohexenes

  摘要：

  An asymmetric organocatalytic [3 + 3] annulation strategy based on a Michael addition/intramolecular Julia-Kocienslci olefination sequence has been developed for the synthesis of 4-substituted-5-nitrocyclohex-1-ene compounds. The strategy is an alternative to the direct reluctant enantioselective Diels-Alder approach. The potential of the methodology has been demonstrated with a concise enantioselective formal synthesis of trandolapril.

  DOI：

  10.1021/jo401686u
• 作为产物：
  描述：

  3-(2,2-dimethoxyethyl)-4-nitro-6-(1-phenyl-1H-tetrazol-5-ylsulfonyl)hexanal 在 caesium carbonate 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 2.25h， 以80%的产率得到
  参考文献：
  名称：

  Organocatalytic Michael Addition/Intramolecular Julia–Kocienski Olefination for the Preparation of Nitrocyclohexenes

  摘要：

  An asymmetric organocatalytic [3 + 3] annulation strategy based on a Michael addition/intramolecular Julia-Kocienslci olefination sequence has been developed for the synthesis of 4-substituted-5-nitrocyclohex-1-ene compounds. The strategy is an alternative to the direct reluctant enantioselective Diels-Alder approach. The potential of the methodology has been demonstrated with a concise enantioselective formal synthesis of trandolapril.

  DOI：

  10.1021/jo401686u

文献信息

• Method for producing (2S,4R,9S)-octahydro-1H-indole-2-carboxylic acid and intermediate products therefor
  申请人：BASF Aktiengesellschaft

  公开号：US06559318B1

  公开（公告）日：2003-05-06

  Described is a process for the preparation of (2S, 4R, 9S)-octahydro-1H-indole-2-carboxylic acid, comprising a) reacting a compound of the formula I (R1O)2CH—CH2—CH(OR2)2  I  wherein R1 and R2 may be the same or different and represent each a C1-4-alkyl group, with water in the presence of an acidic catalyst, b) subjecting the obtained 3,3-dialkoxypropionaldehyde of formula II (R2O)2CH—CH2—CHO  II  to a Henry-reaction with nitromethane, c) subjecting the obtained 4,4-dialkoxy-1-nitro-4-butanol of formula III (R1O)2CH—CH2—CHOH—CH2—NO2  III  to a dehydration d) converting the obtained nitroolefin IV with the aid of a Diels-Alder reaction into the corresponding trans-4-(2,2-dialkoxyethyl)-5-nitro-1-caclohexene V e) hydrogenating the obtained substance V into the corresponding trans-4-(2,2-dialkoxyethyl)-5-amino-1-cyclohexane VI f) subjecting the compound VI to a resolution of racemate and obtaining the (1S, 2R)-1-amino-2-(2,2-dialkoxyethyl)-cyclohexane VII in enantiomerically pure form by enzymatic racemate resolution, g) hydrolysing the obtained compound VII to the corresponding aldehyde VIII h) converting the obtained aldehyde into the corresponding nitrite IX by reaction with cyanide ions and i) saponifying this nitrile to the (2S, 4R, 9S)-octahydro-1H-indole-2-carboxylic acid.

  描述了一种制备(2S, 4R, 9S)-辛氢-1H-吲哚-2-羧酸的过程，包括a)在酸性催化剂存在下，将具有以下结构的化合物与水反应：I(R1O)2CH—CH2—CH(OR2)2，其中R1和R2可以相同也可以不同，分别代表C1-4烷基基团，b)将获得的II(R2O)2CH—CH2—CHO的3,3-二烷氧基丙醛进行亨利反应，c)将获得的III(R1O)2CH—CH2—CHOH—CH2—NO2的4,4-二烷氧基-1-硝基-4-丁醇脱水，d)利用Diels-Alder反应将获得的硝基烯烃IV转化为相应的反式-4-(2,2-二烷氧基乙基)-5-硝基-1-环己烯，e)将获得的物质V氢化为相应的反式-4-(2,2-二烷氧基乙基)-5-氨基-1-环己烷，f)将化合物VI进行外消旋分离，通过酶消旋分离获得对映纯的(1S, 2R)-1-氨基-2-(2,2-二烷氧基乙基)-环己烷VII，g)水解获得的化合物VII得到相应的醛VIII，h)将获得的醛通过与氰根离子反应转化为相应的亚硝酸酯IX，i)皂化此腈得到(2S, 4R, 9S)-辛氢-1H-吲哚-2-羧酸。
• VERFAHREN ZUR HERSTELLUNG VON (2S,4R,9S)-OCTAHYDRO-1H-INDOL-2-CARBONSÄURE UND ZWISCHENPRODUKTE DAFÜR
  申请人：Abbott GmbH & Co. KG

  公开号：EP1140826B1

  公开（公告）日：2004-05-06
• US6559318B1
  申请人：——

  公开号：US6559318B1

  公开（公告）日：2003-05-06
• Organocatalytic Michael Addition/Intramolecular Julia–Kocienski Olefination for the Preparation of Nitrocyclohexenes
  作者：Eduardo Rodrigo、José Luis García Ruano、M. Belén Cid

  DOI：10.1021/jo401686u

  日期：2013.11.1

  An asymmetric organocatalytic [3 + 3] annulation strategy based on a Michael addition/intramolecular Julia-Kocienslci olefination sequence has been developed for the synthesis of 4-substituted-5-nitrocyclohex-1-ene compounds. The strategy is an alternative to the direct reluctant enantioselective Diels-Alder approach. The potential of the methodology has been demonstrated with a concise enantioselective formal synthesis of trandolapril.