methyl (2R,3S)-3-{[(tert-butoxy)carbonyl]amino}-2,5-dimethylhexanoate | 210345-95-2

• 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 (2R,3S)-3-{[(tert-butoxy)carbonyl]amino}-2,5-dimethylhexanoate
• 英文别名: Boc-(2R,3S)-β^2,3-HLeu(α-Me)-OMe
• CAS: 210345-95-2
• 化学式: C₁₄H₂₇NO₄
• 分子量: 273.373
• InChiKey: DFKSOQWCHFJDAD-MNOVXSKESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.73
• 重原子数：
  19.0
• 可旋转键数：
  5.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  64.63
• 氢给体数：
  1.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  methyl (2R,3S)-3-{[(tert-butoxy)carbonyl]amino}-2,5-dimethylhexanoate 在 palladium on activated charcoal tetrabutoxytitanium 、 4 A molecular sieve 、 氢气 、 sodium carbonate 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 、 乙酸乙酯 、 丙酮 为溶剂， 反应 69.5h， 生成 H-(2R,3S)-β^2,3-HAla(α-Me)-(2R,3S)-β²-HVal(α-Me)-(S)-β^2,3-HVal-(S)-β³-HLys-(2R,3S)-β^2,3-HAla-(2R,3S)-β^2,3-HLeu(α-Me)-OH*TFA
  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：

  N-diphenylphosphoryl-3-methyl-1-(4-methylphenyl)sulfonylbutan-1-amine 在 盐酸 、 碳酸氢钠 、 lithium 4-methoxyphenoxide 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 反应 11.83h， 生成 methyl (2R,3S)-3-{[(tert-butoxy)carbonyl]amino}-2,5-dimethylhexanoate
  参考文献：
  名称：

  三氯甲基酮作为合成通用的供体：在直接催化曼尼希型反应和氮杂环丁烷的立体选择性合成中的应用。

  摘要：

  DOI：

  10.1002/anie.200600227

文献信息

• Reaction of α-amidoalkylphenyl sulfones with Reformatsky reagents. A new entry to β-amino esters
  作者：Tiziana Mecozzi、Marino Petrini

  DOI：10.1016/s0040-4039(00)00245-8

  日期：2000.4

  The reaction of Reformatsky reagents with α-amidoalkylphenyl sulfones proceeds in dichloromethane at room temperature leading to the synthesis of the corresponding β-amino esters in good yields. The procedure presents syn stereoselectivity and can be also extended to Reformatsky reagents based on γ-bromocrotonates.

  Reformatsky试剂与α-酰胺基烷基苯基砜的反应在室温下于二氯甲烷中进行，从而以高收率合成了相应的β-氨基酯。该方法具有同构立体选择性，也可以扩展到基于γ-溴巴豆酸盐的Reformatsky试剂。
• ?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).