2,3-二氢-1,4-苯并二噁英-5,6-二胺 | 88501-00-2

• 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
• 中文名称: 2,3-二氢-1,4-苯并二噁英-5,6-二胺
• 中文别名: L-羟脯氨酸苄酯对甲苯磺酸盐
• 英文名称: Hyp-OBzl * p-tolylsulfonic acid
• 英文别名: 4-trans-L-hydroxyproline benzyl ester tosylate；(2S,4R)-4-hydroxyproline benzyl ester p-toluenesulfonate；4-Hydroxy-L-proline benzyl ester p-toluenesulfonate；trans-4-hydroxy-L-proline benzyl ester; toluene-4-sulfonate；(trans)-4-hydroxy-L-proline, phenylmethyl ester, p-toluenesulfonic acid salt；trans-4-Hydroxy-L-prolin-benzylester; Toluol-4-sulfonat；(2S,4R)-4-Hydroxy-proline Benzyl Ester, Toluene Sulfonic Acid Salt；benzyl (2S,4R)-4-hydroxypyrrolidine-2-carboxylate;4-methylbenzenesulfonic acid
• CAS: 88501-00-2
• 化学式: C₇H₈O₃S*C₁₂H₁₅NO₃
• 分子量: 393.461
• InChiKey: YHFQLNADHUYVAF-DHXVBOOMSA-N

物化性质

• 溶解度：
  溶于甲醇

计算性质

• 辛醇/水分配系数(LogP)：
  1.69
• 重原子数：
  27
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  121
• 氢给体数：
  3
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  2,3-二氢-1,4-苯并二噁英-5,6-二胺 在 palladium on activated charcoal 氢气 、 三乙胺 作用下， 以 乙醇 、 N,N-二甲基甲酰胺 、 环己烯 为溶剂， 反应 6.0h， 生成 N-(chloro-2-ethyl)-N-nitrosocarbamyl-L-hydroxyproline
  参考文献：
  名称：

  Montero; Leydet; Messiez-Munoz, European Journal of Medicinal Chemistry, 1984, vol. 19, # 6, p. 512 - 518

  摘要：

  DOI：
• 作为产物：
  描述：

  对甲苯磺酸 、 L-羟基脯氨酸 、 苯甲醇 以 苯 为溶剂， 反应 17.0h， 以96.1%的产率得到2,3-二氢-1,4-苯并二噁英-5,6-二胺
  参考文献：
  名称：

  Catalysis with Phosphine-Containing Amino Acids in Various “Turn” Motifs

  摘要：

  We have been actively involved in the development of parallel approaches for the discovery of phosphine ligands. Our approach has been based on the incorporation of phosphine-containing amino acids into peptide sequences that are designed to have stable secondary structures. We have examined helical and turn secondary structures and have reported that alkylation of cyclopentenyl acetate with dimethylmalonate can be catalyzed in high enantiomeric excess (ee) with a beta-turn-based ligand. The importance of the peptide secondary structure was demonstrated through the synthesis of a series of peptide ligands where the nature of the turn-forming residues was probed. Additionally, other turn-forming units and a variety of different phosphine-containing amino acids have been examined for their ability to control the selectivity of the allylation reaction. This paper reports the results obtained through the examination of different turn motifs as well as different phosphine substitutions on the "best" turn sequence, Pps-Pro-D-Xxx-Pps.

  DOI：

  10.1021/jo049103g

文献信息

• Substituted 4-phenoxy or 4-phenylthio prolines
  申请人：E. R. Squibb & Sons, Inc.

  公开号：US04681886A1

  公开（公告）日：1987-07-21

  This invention is directed to substituted 4-phenoxy and 4-phenylthio prolines of the formula ##STR1## which possess useful hypotensive activity.

  这项发明涉及具有有用的降压活性的式子为##STR1##的取代4-苯氧基和4-苯硫基脯氨酸。
• Regioselective Enolization and Alkylation of 4-Oxo-<i>N</i>-(9-phenylfluoren-9-yl)proline:  Synthesis of Enantiopure Proline−Valine and Hydroxyproline−Valine Chimeras
  作者：Raman Sharma、William D. Lubell

  DOI：10.1021/jo9514984

  日期：1996.1.1

  The regioselective enolization of 4-oxo-N-(9-phenylfluoren-9-yl)proline benzyl ester (5) followed by alkylation with different alkyl halides has been used to synthesize a variety of beta-alkylproline derivatives. In particular, enolization of 5 with 400 mol % of KN(SiMe(3))(2) and alkylation with iodomethane provided 3,3-dimethyl-4-oxo-N-(9-phenylfluoren-9-yl)proline benzyl ester (7a) in excellent yield. Subsequent hydride reduction of ketone 7a and protecting group exchange by hydrogenation in the presence of di-tert-butyl dicarbonate provided enantiopure (2S,4R)- and (2S,4S)-3,3-dimethyl-4-hydroxy-N-(BOC)prolines. 2. Hydroxyproline-valine chimeras (2S,4R)- and (2S,4S)-2 are each synthesized from hydroxyproline in six steps and 27% respective overall yield. Deoxygenation of 3,3-dimethyl-4-hydroxy-N-(9-phenylfluoren-9-yl)proline benzyl esters 9 via their conversion to xanthates 10 followed by tributylstannane-mediated reduction provided 3,3-dimethyl-N-(9-phenylfluoren-9-yl)proline benzyl ester (11) in excellent yield. Hydrogenation of 11 with Pearlman's catalyst in the presence of di-tert-butyl dicarbonate then furnished (2S)-3,3-dimethyl-N-(BOC)proline (1) in the last step of an eight-step synthesis (41% overall yield) from hydroxyproline. Both proline-valine and hydroxyproline-valine chimeras 1 and 2 were designed to serve as tools for studying the conformational requirements of biologically active peptides.
• Kundu, B.; Mathur, K. B., Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 1986, vol. 25, p. 930 - 933
  作者：Kundu, B.、Mathur, K. B.

  DOI：——

  日期：——
• Synthesis of Conformationally Constrained DTPA Analogs. Incorporation of the Ethylenediamine Units as Aminopyrrolidines
  作者：Matthew A. Williams、Henry Rapoport

  DOI：10.1021/jo00092a022

  日期：1994.7

  The synthesis of conformationally constrained diethylenetriaminepentaacetic acid (DTPA) analogues is an effort to probe the relationship between ligand structure and metal complex stability. In the pursuit of this objective, diastereomerically and enantiomerically pure mono- and bis-pyrrolidine analogues of DTPA have been prepared from trans-4-hydroxy-L-proline. The mono-pyrrolidine chelator 1 was constructed from a single hydroxyproline unit and an ethylenediamine moiety while two hydroxyproline-derived fragments 4e or 14b and 9b were coupled by N-alkylation of a triflate to afford the core bis-pyrrolidine structures: optically active 10 and meso-15. Deprotection of the triamine pentaesters 12 and 17 afforded the triamine pentaacetic acids 2 and 3 as their hydrochloride salts. The stereochemical homogeneity of precursor esters 12 and 17 was determined by HPLC using authentic epimeric standards to establish that essentially no racemization of the original amino acid a-center had occurred. Some loss of stereochemical homogeniety was encountered in the synthesis of 10 and 15 by N-alkylation of aminoproline 9b with a hydroxyproline-derived triflate, which had proceeded with some retention of configuration. The diastereomeric impurities were removed by crystallization of the respective benzyl carbamates. Bis-pyrrolidine pentaacids 2 and 3 formed isolable chelates with gadolinium and lutetium. A comparision of the lutetium chelates of 2 and 3 by NMR revealed significant differences which were reflective of a rigid structure with 2, while metal complexation with 3 was structurally less defined.
• Incorporation of fluoroprolines to proctolin: Study on the effect of a fluorine atom toward peptidic conformation
  作者：Takamasa Kitamoto、Taeko Ozawa、Megumi Abe、Shunsuke Marubayashi、Takashi Yamazaki

  DOI：10.1016/j.jfluchem.2007.12.005

  日期：2008.4

  In spite of quite small steric perturbation, substitution of proline (Pro) in the target pentapeptide proctolin (Arg-Tyr-Leu-Pro-Thr) for (4R)- as well as (4S)-4-fluoroproline led to apparent alteration of the pyrrolidine ring structure which eventually resulted in the significant conformational change of the whole molecules which was assumed on the basis of their NOESY spectra. (C) 2008 Elsevier B.V. All rights reserved.