(1S,2R,5S,8R)-5,8,11,11-tetramethyl-3-oxa-6-aza-tricyclo[6.2.1.0^2,7]undec-6-en-4-one | 500137-56-4

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (1S,2R,5S,8R)-5,8,11,11-tetramethyl-3-oxa-6-aza-tricyclo[6.2.1.0^2,7]undec-6-en-4-one
• 英文别名: (1S,2R,5S,8R)-5,8,11,11-tetramethyl-3-oxa-6-azatricyclo[6.2.1.02,7]undec-6-en-4-one
• CAS: 500137-56-4
• 化学式: C₁₃H₁₉NO₂
• 分子量: 221.299
• InChiKey: BYWYJRVGQZJVRE-QARKVSRYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  16
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  38.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3-溴丙烯 、 (1S,2R,5S,8R)-5,8,11,11-tetramethyl-3-oxa-6-aza-tricyclo[6.2.1.0^2,7]undec-6-en-4-one 在 正丁基锂 、 二异丙胺 、 六甲基磷酰三胺 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 13.5h， 以75%的产率得到(1S,2R,5S,8R)-5-allyl-5,8,11,11-tetramethyl-3-oxa-6-azatricyclo[6.2.1.0^2,7]undec-6-en-4-one
  参考文献：
  名称：

  Asymmetric Synthesis of α,α-Disubstituted α-Amino Acids by Diastereoselective Alkylation of Camphor-Based Tricyclic Iminolactone

  摘要：

  A novel and convenient route for the preparation of chiral tricyclic iminolactones 9 and 10 from camphorquinone has been developed. Alkylation of iminolactones 9 and 10 provided iminolactones 16 and 17 in high yields which were, in turn, alkylated again to afford the alpha,alpha-disubstituted products in good yields (70-90%) and excellent diastereoselectivities (> 98%). Hydrolysis of the alkylated iminolactones furnished the desired alpha,alpha-disubstituted alpha-amino acids in good yields and high enantiomeric excesses with good recovery yields of the chiral auxiliary 12 and 13. The extremely high endo-face selectivity for alkylation is discussed using semiempirical (MOPAC 93) calculations.

  DOI：

  10.1021/jo052435g
• 作为产物：
  描述：

  (1R,4S)-2,2:3,3-bis(ethylenedioxy)-1,7,7-trimethylbicyclo[2.2.1]heptane 在 palladium on activated charcoal 4-二甲氨基吡啶 、 sodium tetrahydroborate 、 硫酸 、 水 、 氢气 、 N,N'-二环己基碳二亚胺 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 乙醇 为溶剂， -78.0~20.0 ℃ 、101.33 kPa 条件下， 反应 51.25h， 生成 (1S,2R,5S,8R)-5,8,11,11-tetramethyl-3-oxa-6-aza-tricyclo[6.2.1.0^2,7]undec-6-en-4-one
  参考文献：
  名称：

  Selective Synthesis of Either Enantiomer of α-Amino Acids by Switching the Regiochemistry of the Tricyclic Iminolactones Prepared from a Single Chiral Source

  摘要：

  Preparation of L-alpha-amino acids was easily accomplished simply by exchanging the position of the lactone group of our recently reported chiral template 1 from C-2 to C-3. The new chiral template 7 was prepared in 54% overall yield over five steps from (1R)-(+)-camphor. Alkylation of iminolactone 7 afforded the alpha-monosubstituted products in good yields and excellent diastereoselectivities (>98%). Hydrolysis of the alkylated iminolactones furnished the desired L-alpha-amino acids in good yields and ee with nearly quantitative recovery of chiral auxiliary 4.

  DOI：

  10.1021/jo026285a

文献信息

• Temperature-Dependent Enantio- and Diastereodivergent Synthesis of Amino Acids with One or Multiple Chiral Centers
  作者：Shiming Fan、Shouxin Liu、Sufang Zhu、Juan Feng、Zhiwei Zhang、Jing Huang

  DOI：10.1021/acs.orglett.7b02296

  日期：2017.9.1

  A general and facile methodology for temperature-dependent enantiodivergent and diastereodivergent synthesis of amino acids with one or multiple chiral centers was developed. Camphor-based tricyclic iminolactones attack electrophiles from the endo face at low temperature (−78 to −40 °C) and from the exo face at high temperature (−10 to 25 °C).

  开发了一种通用且简便的方法，用于合成具有一个或多个手性中心的温度依赖性对映异构体和非对映异构体氨基酸。基于樟脑的三环亚氨基内酯在低温（−78至-40°C）时从内表面攻击亲电子体，在高温（−10至25°C）时从外表面攻击亲电子体。
• Total Synthesis of Sphingofungin F Based on Chiral Tricyclic Iminolactone
  作者：Feng-Feng Gan、Shao-Bo Yang、Yong-Chun Luo、Wan-Bang Yang、Peng-Fei Xu

  DOI：10.1021/jo100183d

  日期：2010.4.16

  A new, efficient synthesis of sphingofungin F has been accomplished with 10.4% overall yield in 15 steps. The salient features of the synthesis are the utilization of methyl tricyclic iminolactone 3 for the asymmetric aldol reaction as a key step to introduce two desired stereogenic centers, one-pot reaction for the synthesis of omega-hydroxyketone from epsilon-caprolactone, and an effective one-step deprotection strategy to remove all protecting groups using 0.2 N HCl.
• A concise synthesis of (+)-conagenin and its isomer using chiral tricyclic iminolactones
  作者：Hai-Fei Wang、Guo-Hua Ma、Shao-Bo Yang、Rong-Gang Han、Peng-Fei Xu

  DOI：10.1016/j.tetasy.2008.06.033

  日期：2008.7

  An efficient synthesis of (+)-conagenin, a novel immunomodulator produced by Streptomyces roseosporus, has been achieved via the shortest route at present. At the same time, 2-epiconagenin was synthesized according to the same methodology. (C) 2008 Elsevier Ltd. All rights reserved.
• Asymmetric Synthesis of α,α-Disubstituted α-Amino Acids by Diastereoselective Alkylation of Camphor-Based Tricyclic Iminolactone
  作者：Peng-Fei Xu、Shuo Li、Ta-Jung Lu、Chen-Chang Wu、Botao Fan、Georgia Golfis

  DOI：10.1021/jo052435g

  日期：2006.6.1

  A novel and convenient route for the preparation of chiral tricyclic iminolactones 9 and 10 from camphorquinone has been developed. Alkylation of iminolactones 9 and 10 provided iminolactones 16 and 17 in high yields which were, in turn, alkylated again to afford the alpha,alpha-disubstituted products in good yields (70-90%) and excellent diastereoselectivities (> 98%). Hydrolysis of the alkylated iminolactones furnished the desired alpha,alpha-disubstituted alpha-amino acids in good yields and high enantiomeric excesses with good recovery yields of the chiral auxiliary 12 and 13. The extremely high endo-face selectivity for alkylation is discussed using semiempirical (MOPAC 93) calculations.
• Selective Synthesis of Either Enantiomer of α-Amino Acids by Switching the Regiochemistry of the Tricyclic Iminolactones Prepared from a Single Chiral Source
  作者：Peng-Fei Xu、Ta-Jung Lu

  DOI：10.1021/jo026285a

  日期：2003.1.1

  Preparation of L-alpha-amino acids was easily accomplished simply by exchanging the position of the lactone group of our recently reported chiral template 1 from C-2 to C-3. The new chiral template 7 was prepared in 54% overall yield over five steps from (1R)-(+)-camphor. Alkylation of iminolactone 7 afforded the alpha-monosubstituted products in good yields and excellent diastereoselectivities (>98%). Hydrolysis of the alkylated iminolactones furnished the desired L-alpha-amino acids in good yields and ee with nearly quantitative recovery of chiral auxiliary 4.