4S,5S-1-t-butoxycarbonyl-5-t-butyldiphenylsiloxymethyl-4-vinylpyrrolidine-2-one | 144564-14-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 英文名称: 4S,5S-1-t-butoxycarbonyl-5-t-butyldiphenylsiloxymethyl-4-vinylpyrrolidine-2-one
• 英文别名: (4R,5S)-N-tert-butoxycarbonyl-5-tert-butyldiphenylsiloxymethyl-4-vinylpyrrolidin-2-one；(4R,5S)-1-tert-butyloxycarbonyl-5-((tert-butyldiphenylsilyl)oxymethyl)-4-vinylpyrrolidin-2-one；L-trans-O-(tert-butyldiphenylsilyl)-N-(tert-butyloxycarbonyl)-3-vinyl-pyroglutaminol；(4R,5S)-1-(tert-butoxycarbonyl)-5-(tert-butyldiphenylsilanyloxymethyl)-2-oxo-4-vinylpyrrolidine；tert-butyl (2S,3R)-2-[[tert-butyl(diphenyl)silyl]oxymethyl]-3-ethenyl-5-oxopyrrolidine-1-carboxylate
• CAS: 144564-14-7
• 化学式: C₂₈H₃₇NO₄Si
• 分子量: 479.692
• InChiKey: CQOJOKBWQOXENX-XUZZJYLKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  34
• 可旋转键数：
  9
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  55.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  4S,5S-1-t-butoxycarbonyl-5-t-butyldiphenylsiloxymethyl-4-vinylpyrrolidine-2-one 在 ruthenium(IV) oxide 、 sodium periodate 、 四丁基氟化铵 、 臭氧 作用下， 以 四氢呋喃 、 甲醇 、 四氯化碳 、 二氯甲烷 、 水 、 乙腈 为溶剂， 反应 37.67h， 生成 (4aS,5S)-5-tert-butoxycarbonylamino-2-methyl-3-oxo-2,3,4,4a,5,6-hexahydrofuro[2,3-c]pyridazine
  参考文献：
  名称：

  Investigation of a route to ibotenic acid analogues via a reduced pyroglutamate template

  摘要：

  两种基于 "环切换 "的替代合成方法已被证明可以获得中枢神经系统活性化合物布坦酸的还原保护同手性类似物 27、28 和 36。

  DOI：

  10.1039/b600195e
• 作为产物：
  描述：

  L-焦谷氨酸 在 4-二甲氨基吡啶 咪唑 、 sodium tetrahydroborate 、 正丁基锂 、 氯化亚砜 、 乙醇 、 臭氧 、 lithium chloride 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 36.0h， 生成 4S,5S-1-t-butoxycarbonyl-5-t-butyldiphenylsiloxymethyl-4-vinylpyrrolidine-2-one
  参考文献：
  名称：

  STRUCTURAL MIMETICS OF PROLINE-RICH PEPTIDES AND THE PHARMACEUTICAL USE THEREOF

  摘要：

  该发明涉及一般式（I）的化合物，可用作脯氨酸富集肽的结构模拟体，因此能够结合蛋白质的PRM结合结构域（脯氨酸富集基序结合结构域）。该发明还涉及将这些化合物用作药用活性剂，并将这些药用活性剂用于治疗细菌性疾病、神经退行性疾病和肿瘤。

  公开号：

  US20110034438A1

文献信息

• Addressing Protein-Protein Interactions with Small Molecules: A Pro-Pro Dipeptide Mimic with a PPII Helix Conformation as a Module for the Synthesis of PRD-Binding Ligands
  作者：Jan Zaminer、Christoph Brockmann、Peter Huy、Robert Opitz、Cédric Reuter、Michael Beyermann、Christian Freund、Matthias Müller、Hartmut Oschkinat、Ronald Kühne、Hans-Günther Schmalz

  DOI：10.1002/anie.201001739

  日期：2010.9.17

  be incorporated, without loss of binding ability, as a Pro‐Pro substitute into two peptides that bind to the proline‐rich motif‐recognizing domains Fyn‐SH3. The dipeptide analogue X, which is locked in a polyproline type II helix conformation, is created by stereoselective introduction of a vinylidene bridge into a diproline unit.

  X标记斑点：可以将合成的三环氨基酸X（见结构； C灰色，H青色，N蓝色，O红色，双键黄色）并入Pro-Pro替代品中，而不会失去结合能力，成为两个肽与富含脯氨酸的基序识别结构域Fyn-SH3结合。通过将亚乙烯基桥立体选择性地引入到双脯氨酸单元中，可以生成被锁定在II型多脯氨酸螺旋构象中的二肽类似物X。
• Molecular Building Kit of Fused-Proline-Derived Peptide Mimetics Allowing Specific Adjustment of the Dihedral Ψ Angle
  作者：Juergen Einsiedel、Harald Lanig、Reiner Waibel、Peter Gmeiner

  DOI：10.1021/jo701703e

  日期：2007.11.1

  [Graphics]Proline-derived peptide mimetics have become an area of paramount importance in peptide and protein chemistry. Since protein crystal structures frequently display W angles of 140-170 degrees for prolyl moieties, our intention was to design a completely novel series of 2,3-fused-proline-derived lactams covering this particular conformational space. Extending our recently described toolset of spirocyclic reverse-turn mimetics, we synthesized pyrrolidinyl-fused seven-, eight-, and nine-membered unsaturated lactam model peptides taking advantage of Grubbs' ring-closing metathesis. Investigating the seven-membered lactam 3a by means of IR and NMR spectroscopy and semiempirical molecular dynamics simulations, we could not observe a U-turn conformation; however, increasing the ring size to give eight- and nine-membered congeners revealed moderate and high type II P-turn inducing properties. Interestingly, the conformational properties of our model systems depend on both the ring size of the fused dehydro-Freidinger lactam and the position of the endocyclic double bond. Superior reverse-turn inducing properties could be observed for the fused azacyclononenone 3e. According to diagnostic transanular NOEs, a discrete folding principle of the lactam ring strongly deviating from the regioisomeric lactams 3c,f explains the conformational behavior. Hence, we were able to establish a molecular building kit that allows adjustments of a wide range of naturally occurring proline W angles and thus can be exploited to probe molecular recognition and functional properties of biological systems.
• Synthesis of homochiral R-Baclofen from S-glutamic acid.
  作者：C. Herdeis、H.P. Hubmann

  DOI：10.1016/s0957-4166(00)82107-2

  日期：1992.9

  A stereoselective synthesis of R-Baclofen is presented, starting from S-pyroglutamic acid derivative 3. The key steps are the 1,4-conjugate addition of Grignard cuprate (p-ClPh)2CuMgCl to 3 and Barton-Decarboxylation of 6e to 7e.
• Synthesis of homochiral 3-substituted glutamic acids and prolines from pyroglutamic acid
  作者：Claus Herdeis、Hans Peter Hubmann、Hermann Lotter

  DOI：10.1016/s0957-4166(00)86204-7

  日期：1994.3

  Efficient syntheses of (2S,3S)-methylproline (5a) and (2S,3R)-phenylproline (5b) are described, starting from the readily available pyroglutaminol derivatives 2a and 2b via conjugate 1-4-addition of organocuprates to 1. Catalytic hydrogenation of 3 from the least hindered alpha-side furnishes 6, which is transformed to (2S,3R)-methylproline (7). 3-Substituted glutamic acids 8c,d are provided by a four step procedure from 2c,d.