2',1':1,2;1'',2'':3,4-dinaphthcyclohepta-1,3-diene-6-aminomethyl-6-carboxylic acid ethyl ester | 232266-13-6

• 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 ethyl ester
• 英文别名: Ethyl 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；ethyl 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
• CAS: 232266-13-6
• 化学式: C₂₇H₂₅NO₂
• 分子量: 395.501
• InChiKey: LLZRRTRODLUJGI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.4
• 重原子数：
  30
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.22
• 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 ethyl ester 在 sodium hydroxide 、 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 、 甲醇 、 二氯甲烷 、 水 、 乙腈 为溶剂， 反应 4.0h， 生成 4-(Benzoylamino-methyl)-4,5-dihydro-3H-cyclohepta[2,1-a;3,4-a']dinaphthalene-4-carboxylic acid ((S)-1-cyclohexylcarbamoyl-2-phenyl-ethyl)-amide
  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-cyano-6-carboxylic acid ethyl ester 在 sodium tetrahydroborate 、 cobalt(II) chloride 作用下， 以 四氢呋喃 、 甲醇 、 水 为溶剂， 反应 2.0h， 以53%的产率得到2',1':1,2;1'',2'':3,4-dinaphthcyclohepta-1,3-diene-6-aminomethyl-6-carboxylic acid ethyl 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 α,α-disubstituted-β-aminoacids with axial chirality
  作者：Anne Gaucher、Fabrice Bintein、Michel Wakselman、Jean-Paul Mazaleyrat

  DOI：10.1016/s0040-4039(97)10704-3

  日期：1998.2

  6-aminomethyl-6,7-dihydro-5H-dibenzo[a,c]cycloheptene-6-carboxylic acid ethyl ester H-beta(2)-Bip-OEt 1a and its 1,1'-binaphthyl optically pure analog (R) H-beta(2)-Bin-OEt 2a have been readily synthesized by bis-alkylation of ethyl cyanoacetate with 2,2'-bis-(bromomethyl)-1,1'-diphenyl or optically pure (+)-(R)-2,2'-bis-(bromomethyl)-1,1'-binaphthyl, followed by NaBH4/CoCl2 selective reduction of the cyano group. The N-Boc protected derivatives and short peptides of these novel aminoacids have also been prepared (C) 1998 Elsevier Science Ltd. All rights reserved.
• Synthesis and resolution of β2,2-HBin, the first enantiomerically stable β-amino acid with chirality only due to axial dissymmetry
  作者：Anne Gaucher、Yohan Zuliani、Daniel Cabaret、Michel Wakselman、Jean-Paul Mazaleyrat

  DOI：10.1016/s0957-4166(01)00435-9

  日期：2001.10

  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.