methyl (2R,3S)-3-{[(tert-butoxy)carbonyl]amino}-2,4-dimethylpentanoate | 210345-93-0

• 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 (2R,3S)-3-{[(tert-butoxy)carbonyl]amino}-2,4-dimethylpentanoate
• 英文别名: methyl (2R, 3S)-3-((tert-butoxycarbonyl)amino)-2,4-dimethylpentanoate；Boc-(2R,3S)-β^2,3-HVal(α-Me)-OMe；methyl (2R,3S)-2,4-dimethyl-3-[(2-methylpropan-2-yl)oxycarbonylamino]pentanoate
• CAS: 210345-93-0
• 化学式: C₁₃H₂₅NO₄
• 分子量: 259.346
• InChiKey: LLIRGAMWGANOJB-ZJUUUORDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  18
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.85
• 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 (2R,3S)-3-{[(tert-butoxy)carbonyl]amino}-2,4-dimethylpentanoate 在 palladium on activated charcoal tetrabutoxytitanium 、 4 A molecular sieve 、 氢气 作用下， 以 甲醇 为溶剂， 反应 55.0h， 生成 (2R,3S)-3-{[(tert-butoxy)carbonyl]amino}-2,4-dimethylpentanoic acid
  参考文献：
  名称：

  Structure and Conformation ofβ-Oligopeptide Derivatives with Simple Proteinogenic Side Chains: Circular Dichroism and Molecular Dynamics Investigations

  摘要：

  DOI：

  10.1002/(sici)1522-2675(20000119)83:1<34::aid-hlca34>3.0.co;2-b
• 作为产物：
  描述：

  (4S)-4-benzyl-3-(3-(benzylamino)-2,4-dimethylpentanoyl)oxazolidin-2-one 在 4-二甲氨基吡啶 、 palladium on activated charcoal 、 三乙胺 作用下， 以 四氢呋喃 为溶剂， 20.0 ℃ 、101.33 kPa 条件下， 反应 32.5h， 生成 methyl (2R,3S)-3-{[(tert-butoxy)carbonyl]amino}-2,4-dimethylpentanoate
  参考文献：
  名称：

  钠化 Evans 烯醇化物的结构和反应性：溶剂化和混合聚集对烷基化立体化学和机理的作用

  摘要：

  在 N,N,N',N'-四甲基乙二胺 (TMEDA)、(R,R)-反式-存在下，使用二异丙基酰胺钠 (NaDA) 或六甲基二硅肼钠 (NaHMDS) 生成基于恶唑烷酮的钠化烯醇化物 (Evans enolates) N,N,N',N'-四甲基环己二胺 [(R,R)-TMCDA] 或 (S,S)-TMCDA。13C NMR 光谱分析结合连续变化法 (MCV)、X 射线晶体学和密度泛函理论 (DFT) 计算表明烯醇化物是八面体双二胺螯合单体。烯丙基溴烷基化的速率和计算研究表明基于双二胺螯合单体的过渡结构。钠化的 Evans 烯醇化物与 NaHMDS、NaDA 或 2,6-二叔丁基苯酚钠形成混合二聚体，检查其反应性。

  DOI：

  10.1021/jacs.8b10364

文献信息

• ?2- and ?3-Peptides with Proteinaceous Side Chains: Synthesis and solution structures of constitutional isomers, a novel helical secondary structure and the influence of solvation and hydrophobic interactions on folding
  作者：Dieter Seebach、Stefan Abele、Karl Gademann、Gilles Guichard、Tobias Hintermann、Bernhard Jaun、Jennifer L. Matthews、J�rg V. Schreiber、Lukas Oberer、Ulrich Hommel、Hans Widmer

  DOI：10.1002/hlca.19980810513

  日期：——

  the previously prepared β-peptides (35–39) showed NH/ND exchange rates (in MeOH at room temperature) with τ1/2 values of up to 60 days, unrivalled by short chain α-peptides. All β-peptides 1–7 were designed to be able to attain the previously described 31-helical structure (Figs. 1 and 2). CD Measurements (Fig. 4), indicating a new secondary structure of certain β-peptides constructed of β2- and β3-amino

  对映体纯β-氨基酸为Ala，Val取代，和Leu的在2-或3-位上的侧链的衍生物（β 2 -和β 3 -氨基酸，RESP），以及与在这两个取代基2-位和3-位（β 2,3 -氨基酸的，像-构型）已经制备（化合物8 - 17）和结合（通过逐步合成和片段耦合，中间体24 - 34）到β-化十六- ， β-庚肽和β-十二肽（1 – 17）。新的和一些先前制备的β肽（35 – 39）显示了NH / ND交换速率（室温下在MeOH中），其τ1 /2值长达60天，这是短链α肽无法比拟的。所有的β肽1至7被设计为能够获得先前描述的3 1螺旋结构（图1和2）。CD测量（图4），表明β的构建某些β肽的新的二级结构2 -和β 3 -氨基酸，通过详细的NMR溶液结构分析确认：一个β 2 -heptapeptide（2C）和β 2,3- -hexapeptide（图7c），由于具有3 1螺旋结构（图6和7），而到β
• ——
  作者：Dieter Seebach、Thierry Sifferlen、Daniel J. Bierbaum、Magnus Rueping、Bernhard Jaun、Bernd Schweizer、Jacob Schaefer、Anil K. Mehta、Robert D. O'Connor、Beat H. Meier、Matthias Ernst、Alice Glättli

  DOI：10.1002/1522-2675(200209)85:9<2877::aid-hlca2877>3.0.co;2-w

  日期：2002.9

  The preparation of (S)-beta(2.2.3) -amino acids with two Me groups in the a-position and the side chains of Ala, Val, and Len in the P-position (double methylation of Boc-beta-HAla-OMe, Boc-beta-Val-OMe, and Boc-beta-LeuOMe, Scheme 2) is described. These beta-amino acids and unlabelled as well as specifically C-13- and (15)labelled 2,2-dimethyl-3-amino acid (beta(2.2)-HAib) derivatives have been coupled in solution (Schemes 1, 3 and 4) to give protected (N-Boc, C-OMe), partially protected (N-Boc/C-OH, N-H/C-OMe), and unprotected beta(2.2) - and beta(2.2.3)- hexapeptides, and beta(2.2) and beta(2.2.3)-heptapeptides 1-7. NMR Analyses in solution (Tables 1 and 2, and Figs. 2-4) and in the solid state (2D-MAS NMR measurements of the fully labelled BOC-(beta(2.2)-HAib)(6)-OMe ([C-13(30), N-15(6)]-1e; Fig. 5), and TEDOR/REDOR NMR investigations of mixtures (Fig. 6) of the unlabelled AC-([beta(2.2)-HAib)(7)- OMe (4) and of a labelled derivative ([C-13(4),N-15(2)]-5; Figs. 7- 11, and 19), a molecular-modeling study (Figs. 13 15), and a search in the Cambridge Crystallographic Data Base (Fig. 16) allow the following conclusions: i) there is no evidence for folding (helix or turn) or for aggregation to sheets of the geminally dimethyl substituted peptide chains in solution; ii) there are distinct conformational preferences of the individual beta(2.2) and beta(2.2.3)-amino acid residues: close to eclipsing around the C(O) - C(Me-2(CHR)) bond (tau(1.2)), almost perfect staggering around the C(2)-C(3) ethane bond (tau(2,3)), and antiperiplanar arrangement of H(C3) and H(N) (TIN; Fig. 12) in the solid state; iii) the beta(2,2)-peptides may be part of a turn structure with a ten-membered H-bonded ring; iv) the main structure present in the solid state of F3CCO(beta(2,2) -HAib)(7)-OMe is a nonfolded chain (>30 Angstrom between the termini and >20 Angstrom between the N-terminus and the CH2 group of residue 5) with all C = O bonds in a parallel alignment (+/-10degrees). With these structural parameters, a simple modelling was performed producing three (maybe four) possible chain geometries: one fully extended, two with parallel peptide planes (with zick-zack and crankshaft-type arrangement of the peptide bonds). and (possibly) a fourth with meander-like winding (D-G in Figs. 17 and 18).
• 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).
• Structure and Conformation ofβ-Oligopeptide Derivatives with Simple Proteinogenic Side Chains: Circular Dichroism and Molecular Dynamics Investigations
  作者：Dieter Seebach、Jürg V. Schreiber、Stefan Abele、Xavier Daura、Wilfred F. van Gunsteren

  DOI：10.1002/(sici)1522-2675(20000119)83:1<34::aid-hlca34>3.0.co;2-b

  日期：2000.1.19
• Structures and Reactivities of Sodiated Evans Enolates: Role of Solvation and Mixed Aggregation on the Stereochemistry and Mechanism of Alkylations
  作者：Zirong Zhang、David B. Collum

  DOI：10.1021/jacs.8b10364

  日期：2019.1.9

  crystallography, and density functional theory (DFT) computations revealed the enolates to be octahedral bis-diamine-chelated monomers. Rate and computational studies of an alkylation with allyl bromide implicate a bis-diamine-chelated-monomer-based transition structure. The sodiated Evans enolates form mixed dimers with NaHMDS, NaDA, or sodium 2,6-di- tert-butylphenolate, the reactivities of which

  在 N,N,N',N'-四甲基乙二胺 (TMEDA)、(R,R)-反式-存在下，使用二异丙基酰胺钠 (NaDA) 或六甲基二硅肼钠 (NaHMDS) 生成基于恶唑烷酮的钠化烯醇化物 (Evans enolates) N,N,N',N'-四甲基环己二胺 [(R,R)-TMCDA] 或 (S,S)-TMCDA。13C NMR 光谱分析结合连续变化法 (MCV)、X 射线晶体学和密度泛函理论 (DFT) 计算表明烯醇化物是八面体双二胺螯合单体。烯丙基溴烷基化的速率和计算研究表明基于双二胺螯合单体的过渡结构。钠化的 Evans 烯醇化物与 NaHMDS、NaDA 或 2,6-二叔丁基苯酚钠形成混合二聚体，检查其反应性。