2',1':1,2;1'',2'':3,4-dinaphthcyclohepta-1,3-diene-6-aminomethyl-6-carboxylic acid methyl ester

• 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: 2',1':1,2;1'',2'':3,4-dinaphthcyclohepta-1,3-diene-6-aminomethyl-6-carboxylic acid methyl ester
• 英文别名: Methyl 13-(aminomethyl)pentacyclo[13.8.0.02,11.03,8.018,23]tricosa-1(15),2(11),3,5,7,9,16,18,20,22-decaene-13-carboxylate；methyl 13-(aminomethyl)pentacyclo[13.8.0.02,11.03,8.018,23]tricosa-1(15),2(11),3,5,7,9,16,18,20,22-decaene-13-carboxylate
• 化学式: C₂₆H₂₃NO₂
• 分子量: 381.474
• InChiKey: PRQUJOXEALRRQR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  29
• 可旋转键数：
  3
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  52.3
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2',1':1,2;1'',2'':3,4-dinaphthcyclohepta-1,3-diene-6-aminomethyl-6-carboxylic acid methyl ester 在 sodium hydroxide 作用下， 以 甲醇 、 水 、 乙腈 为溶剂， 反应 4.0h， 生成 2',1':1,2;1'',2'':3,4-dinaphthcyclohepta-1,3-diene-6-N-tert-butyloxycarbonylaminomethyl-6-carboxylic acid
  参考文献：
  名称：

  Synthesis and resolution of β2,2-HBin, the first enantiomerically stable β-amino acid with chirality only due to axial dissymmetry

  摘要：

  The first gem-disubstituted beta (2.2)-amino acid possessing only axial chirality, was synthesized by bis-alkylation of methyl or ethyl cyanoacetate with both racemic and enantiomerically pure (R)-2,2'-bis-(bromomethyl)-1,1'-binaphthyl, followed by NaBH4/CoCl2 reduction of the cyano group, treatment of the resulting amino esters with Boc(2)O and finally saponification of thc ester function, to afford the C- and/or N-protected derivatives of 2',1':1,2,1".2":3,4-dinaphthcyclohepta-1,3-diene-6-aminomethyl-6-carboxylic acid: (RS)- and (R)-X-beta (2.2)-HBin-OR (X = Boc: H) (R = Me. Et or H). For the medium-scale resolution of beta (2.2)-HBin. the racemic amino esters (RS)-H-beta (2.2)-HBin-OR (R= Me. Et) were treated with benzoic anhydride and the resulting derivatives (RS)-Bz-beta (2.2)-HBin-OR were saponified, The obtained (RS)-Bz-beta (2.2)-HBin-OH was coupled with L-phenylalanine cyclohexylamide by the EDC/HOBt method to afford the dipeptide diastereoisomers Bz-(R)-Bin-L-Phe-NH-C6H11 and Bz-(S)-Bin-L-Phe-NH-C6H11, which were separated by chromatography. Complete hydrolysis under acidic conditions. followed by esterification of the resulting free amino acid enantiomers, N-protection and saponification, led to the enantiomerically pure derivatives (R)- and (S)-X-beta (2.2)-HBin-OR (X=Boc-H) (R=Me, H). (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(01)00435-9
• 作为产物：
  描述：

  2',1':1,2;1'',2'':3,4-dinaphthcyclohepta-1,3-diene-6-N-benzoylaminomethyl-6-carboxylic acid ethyl ester 在 盐酸 、 sodium hydroxide 、 硫酸 、 1-羟基苯并三唑 、 盐酸-N-乙基-Nˊ-(3-二甲氨基丙基)碳二亚胺 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 甲醇 、 二氯甲烷 、 水 为溶剂， 反应 244.0h， 生成 2',1':1,2;1'',2'':3,4-dinaphthcyclohepta-1,3-diene-6-aminomethyl-6-carboxylic acid methyl ester
  参考文献：
  名称：

  Synthesis and resolution of β2,2-HBin, the first enantiomerically stable β-amino acid with chirality only due to axial dissymmetry

  摘要：

  The first gem-disubstituted beta (2.2)-amino acid possessing only axial chirality, was synthesized by bis-alkylation of methyl or ethyl cyanoacetate with both racemic and enantiomerically pure (R)-2,2'-bis-(bromomethyl)-1,1'-binaphthyl, followed by NaBH4/CoCl2 reduction of the cyano group, treatment of the resulting amino esters with Boc(2)O and finally saponification of thc ester function, to afford the C- and/or N-protected derivatives of 2',1':1,2,1".2":3,4-dinaphthcyclohepta-1,3-diene-6-aminomethyl-6-carboxylic acid: (RS)- and (R)-X-beta (2.2)-HBin-OR (X = Boc: H) (R = Me. Et or H). For the medium-scale resolution of beta (2.2)-HBin. the racemic amino esters (RS)-H-beta (2.2)-HBin-OR (R= Me. Et) were treated with benzoic anhydride and the resulting derivatives (RS)-Bz-beta (2.2)-HBin-OR were saponified, The obtained (RS)-Bz-beta (2.2)-HBin-OH was coupled with L-phenylalanine cyclohexylamide by the EDC/HOBt method to afford the dipeptide diastereoisomers Bz-(R)-Bin-L-Phe-NH-C6H11 and Bz-(S)-Bin-L-Phe-NH-C6H11, which were separated by chromatography. Complete hydrolysis under acidic conditions. followed by esterification of the resulting free amino acid enantiomers, N-protection and saponification, led to the enantiomerically pure derivatives (R)- and (S)-X-beta (2.2)-HBin-OR (X=Boc-H) (R=Me, H). (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(01)00435-9

文献信息

• Synthesis of linear and cyclic homo-β-peptides based on a binaphthylic β-amino acid with only axial chirality
  作者：Anne Gaucher、Laurence Dutot、Olivier Barbeau、Michel Wakselman、Jean-Paul Mazaleyrat、Cristina Peggion、Simona Oancea、Fernando Formaggio、Marco Crisma、Claudio Toniolo

  DOI：10.1016/j.tetasy.2005.11.021

  日期：2006.1

  The terminally protected, linear, homo-β-peptides Boc-[(R)-β2,2-HBin]n-OMe (n = 2–6) as well as the cyclic homo-β-peptides c[(R)-β2,2-HBin]3 and c[(S)-β2,2-HBin]4, all derived from the 2′,1′:1,2;1″,2″:3,4-dinaphthcyclohepta-1,3-diene-6-aminomethyl-6-carboxylic acid residue β2,2-HBin possessing only axial chirality, have been synthesized in solution by the EDC/AtOH coupling method for chain elongation

  的末端保护的，直链的，HOMO-β肽的Boc - [（[R）-β 2,2 -HBin] Ñ -OMe（Ñ  = 2-6）以及作为环状HOMO-β肽C [（[R ） -β 2,2 -HBin] 3和c [（小号）-β 2,2 -HBin] 4，所有从2'，1'导出：1,2; 1“，2”：3,4-dinaphthcyclohepta -1,3-二烯-6-氨基甲基-6-羧酸残基β2,2-HBin仅具有轴向手性，已在溶液中通过EDC / AtOH偶联方法进行链延长和五氟苯基酯环化合成。构象分析表明溶液中线性低聚物会同时发生不同的分子内氢键形式。