methyl 3-(R)-[N-(tert-butoxycarbonyl)amino]-4-methylpentanoate | 511550-54-2

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: methyl 3-(R)-[N-(tert-butoxycarbonyl)amino]-4-methylpentanoate
• 英文别名: (S)-methyl 3-(tert-butoxycarbonyl)-4-methylpentanoate；Boc-(S)-β3hVal methyl ester；methyl (S)-3-((tert-butoxycarbonyl)amino)-4-methylpentanoate；methyl (3S)-4-methyl-3-[(2-methylpropan-2-yl)oxycarbonylamino]pentanoate
• CAS: 511550-54-2
• 化学式: C₁₂H₂₃NO₄
• 分子量: 245.319
• InChiKey: HJFMEBROZSGPLZ-VIFPVBQESA-N

物化性质

• 沸点：
  329.6±25.0 °C(Predicted)
• 密度：
  1.008±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  17
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  64.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  methyl 3-(R)-[N-(tert-butoxycarbonyl)amino]-4-methylpentanoate 在 lithium hydroxide 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 1.0h， 以89%的产率得到S-3-Boc-氨基-4-甲基戊酸
  参考文献：
  名称：

  A Convenient Synthesis of Chiral β³-Amino Acids

  摘要：

  开发了一种合成手性β3-氨基酸的新方法，其中酸功能团是通过氧化断裂引入的α-烯丙基，该基团由Evans不对称烷基化适当的酸底物引入，而氨基部分则来自原始羧基的酰胺，经过改良的Hofmann重排反应后形成。

  DOI：

  10.1055/s-2002-35608
• 作为产物：
  描述：

  异丁酰醋酸甲酯 在 [Ph(COD)Cl]2 (R,S)-tert-butyl Josiphos 、 ammonium acetate 、 氢气 作用下， 以 甲醇 为溶剂， 20.0~50.0 ℃ 、689.47 kPa 条件下， 反应 42.0h， 生成 methyl 3-(R)-[N-(tert-butoxycarbonyl)amino]-4-methylpentanoate
  参考文献：
  名称：

  检测和消除烯胺的不对称催化氢化产生的产物抑制作用。

  摘要：

  [反应：见正文]通过动力学研究表明，由二茂铁基配体1a或1b和[（COD）RhCl]（2）制备的用催化剂Rh-1a催化烯胺酰胺和酯的催化不对称加氢反应抑制。还显示烯胺酯底物与在甲醇中反应的胺产物不相容。用二碳酸二叔丁酯原位保护胺产物消除了酯底物的官能团不相容性，并消除了反应中产物的抑制作用。

  DOI：

  10.1021/ol051862d

文献信息

• Catalytic Asymmetric Mannich Reactions of Sulfonylacetates
  作者：Carlo Cassani、Luca Bernardi、Francesco Fini、Alfredo Ricci

  DOI：10.1002/anie.200900701

  日期：2009.7.20

  synthetic equivalents of a variety of α‐carboxylate anions. Phase‐transfer catalysis (PTC) enabled their mild deprotonation and catalytic asymmetric addition to highly reactive imines generated in situ from α‐amidosulfones (see scheme; Pg=protecting group). The synthetic utility of the products was demonstrated by their straightforward transformation into a range of β‐amino acid derivatives.

  砜与砜：芳基磺酰乙酸盐可以看成是各种α-羧酸根阴离子的合成等价物。相转移催化（PTC）使它们能够轻度去质子化，并催化不对称添加到α-酰胺基砜现场生成的高反应性亚胺上（见方案； Pg =保护基）。通过将其直接转化为一系列β-氨基酸衍生物，证明了该产品的合成效用。
• Synthesis and Conformation of Fluorinated β-Peptidic Compounds
  作者：Victoria Peddie、Raymond J. Butcher、Ward T. Robinson、Matthew C. J. Wilce、Daouda A. K. Traore、Andrew D. Abell

  DOI：10.1002/chem.201200313

  日期：2012.5.21

  that, for α‐fluoroamides, the FCC(O)N(H) moiety adopts an antiperiplanar conformation. In addition, a gauche conformation is favoured between the vicinal CF and CN(CO) bonds in N‐β‐fluoroethylamides. This study details the synthesis of a series of fluorinated β‐peptides (1–8) designed to use these stereoelectronic effects to control the conformation of β‐peptide bonds. X‐ray crystal structures of

  实验和理论数据表明，对于α-fluoroamides中，F  Ç  C（O） N（H）部分的采用antiperiplanar构象。另外，在N -β-氟代乙酰胺中，邻位的CF和CN（CO）键之间存在gauche构象。本研究中详细介绍了一系列氟化β肽（的合成1 - 8）设计为使用这些立体电子效应来控制β肽键的构象。这些化合物的X射线晶体结构揭示了预期的构象：用氟β到氮采用笨拙构象，并且氟α至C ＝ O基团采用反平面构象。因此，氟的战略位置可以控制β肽键的构象，并有可能指导β肽的二级结构。
• Optimization of the β-Aminoester class of factor Xa inhibitors. part 1: P4 and side-Chain modifications for improved In vitro potency
  作者：Mark Czekaj、Scott I Klein、Kevin R Guertin、Charles J Gardner、Allison L Zulli、Henry W Pauls、Alfred P Spada、Daniel L Cheney、Karen D Brown、Dennis J Colussi、Valeria Chu、Robert J Leadley、Christopher T Dunwiddie

  DOI：10.1016/s0960-894x(02)00212-3

  日期：2002.6

  A systematic modification of the C3 side-chain of the beta-aminoester class of factor Xa inhibitors and a survey Of P-4 variations is described. These changes have resulted in the identification of sub-nanomolar inhibitors with improved selectivity versus related proteases. Coagulation parameters (i.e., APTT doubling concentrations) are also improved. (C) 2002 Elsevier Science Ltd. All rights reserved.
• CD Spectra in Methanol ofβ-Oligopeptides Consisting ofβ-Amino Acids with Functionalized Side Chains, with Alternating Configuration, and with Geminal Backbone Substituents - Fingerprints of New Secondary Structures?
  作者：Dieter Seebach、Thierry Sifferlen、Pascal A. Mathieu、Andreas M. Häne、Christoph M. Krell、Daniel J. Bierbaum、Stefan Abele

  DOI：10.1002/1522-2675(20001108)83:11<2849::aid-hlca2849>3.0.co;2-r

  日期：2000.11.8

  beta -Hexa-, beta -hepta-, and beta -nonapeptides, 1-6, which carry functionalized side chains (CO(2)R, CO(2)(-), (CH(2))(4)NH(3)(+), CH(2)-CH=CH(2)) consisting of beta (3)-amino-acid residues of alternating configuration, or which carry geminal substituents in the 2- or 3-positions of all residues, have been synthesized (Schemes 1 - 3), and their CD spectra in MeOH are reported (Figs. 2 - 6). Strong Cotton effects (Theta >10(5)) are indicative of the presence of chiral secondary structures. It is suggested by simple modelling (Fig. 1) that the new beta -peptides should not be able to fold to the familiar 3(14)-helical structures. Still, three of them (3, 4, and 5) give rise to CD spectra matching those of beta -peptides that are known to be present as (M)- or (P)3(14)-helices in MeOH solution. While possible folding motifs (Figs. 3, b, and 7) of the new beta -peptides have been identified in crystal structures, an interpretation of the CD spectra has to be postponed until NMR solution structures become available. A list of all beta -peptides giving rise to CD spectra with a minimum near 215 nm is included (Table).