(S)-(E)-2-methyl-hex-4-enal | 104372-55-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (S)-(E)-2-methyl-hex-4-enal
• 英文别名: (2S,4E)-2-methyl-4-hexenal；(E,2S)-2-methylhex-4-enal
• CAS: 104372-55-6
• 化学式: C₇H₁₂O
• 分子量: 112.172
• InChiKey: QGHYUPCCGBNRMU-SDLBARTOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  8
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (S)-(E)-2-methyl-hex-4-enal 在 N-乙基哌啶 、 tin(II) trifluoromethanesulfonate 作用下， 以 甲醇 、 乙醚 为溶剂， 反应 1.55h， 生成 methyl (4S,5R)-5-((1'S,3'E)-1'-methyl-3'-pentenyl)-2-thioxooxazolidine-4-carboxylate
  参考文献：
  名称：

  Synthesis, biological activity, and conformational analysis of (2S,3R,4S)-MeBmt-cyclosporin, a novel 1-position epimer of cyclosporin A

  摘要：

  Cyclosporin A (CsA, 1), an immunosuppressive cyclic undecapeptide, contains a unique amino acid, (4R)-4-[(E)-butenyl]-4,N-dimethyl-L-threonine (MeBmt), that appears to be critically involved in the biological activity of CsA. In order to further explore the effect that structural elements in MeBmt have on the conformation and biological activity of CsA, the 4-epimer of MeBmt [(4S)-MeBmt, 2] and the corresponding CsA analogue [(4S)-MeBmt1-CsA, 3] have been synthesized. Biological assay using concanavalin A stimulated thymocytes indicated that (4S)-MeBmt1-CsA (3) has only 2-4% immunosuppressive activity relative to CsA. The NMR analysis by 1D and 2D NMR methods establishes the conformation of 3, of which the 33-membered cyclic peptide ring system in chloroform is very similar to that of CsA. However, the NMR analysis also reveals that the 1-position side chain orientation in (4S)-MeBmt1-CsA (3) is very different from that of CsA. Specifically, the (4S)-MeBmt alpha,beta-torsion angle (chi 1) has been rotated approximately 120 degrees relative to that of CsA, and the orientation of the butenyl side chain relative to the 33-membered peptide backbond is different. The orientation of the (4S)-MeBmt side chain is consistent with the possible conformations calculated for (4S)-MeBmt1-CsA (3) by using molecular mechanics (in vacuo) calculations. The conformational analysis suggests that the loss of biological activity for 3 results from an altered conformation of the 1-position side chain relative to the peptide backbond due to the changed chirality at C4 of MeBmt.

  DOI：

  10.1021/jm00128a048
• 作为产物：
  描述：

  (S,E)-2-methylhex-4-en-1-ol 在 2-碘酰基苯甲酸 作用下， 以 二甲基亚砜 为溶剂， 反应 0.5h， 生成 (S)-(E)-2-methyl-hex-4-enal
  参考文献：
  名称：

  强力免疫抑制剂吡罗宁的全合成

  摘要：

  PA-48153C吡咯丁酮的全合成-一种有效的免疫抑制剂。

  DOI：

  10.1016/0040-4039(96)01413-x

文献信息

• Asymmetric glycine enolate aldol reactions: synthesis of cyclosporin's unusual amino acid, MeBmt
  作者：David A. Evans、Ann E. Weber

  DOI：10.1021/ja00281a049

  日期：1986.10

  Synthese de l'acide (hydroxy-3 methyl-4 methylamino-2) octene-6oique apr aldolisation entre l'enolate de la (benzyl-4 isothiocyanatoacetyl-3) oxazolidone-2 et des alcenals

  合成 de l'acide (hydroxy-3methyl-4methylamino-2) octene-6oique apr aldolisation entre l'enolate de la (benzyl-4 isothiocyanatoacetyl-3) oxazolidone-2 et des alcenals
• Biosynthesis of tetronasin: Part 3 preparation of deuterium labelled tri- and tetraketides as putative biosynthetic precursors of tetronasin
  作者：Helen C. Hailes、Sandeep Handa、Peter F. Leadlay、Ian C. Lennon、Steven V. Ley、James Staunton

  DOI：10.1016/s0040-4039(00)76541-5

  日期：1994.1

  The preparation of seven deuterium labelled N-acetyl cysteamine thioesters (2a), (2b), (3a), (3b), (4), (5) and (6) as putative biosynthesis precursors of the acyl tetronic acid ionophore tetronasin is described.

  七个氘标记的N-乙酰半胱胺硫代酸酯（2a），（2b），（3a），（3b），（4），（5）和（6）的制备是酰基四氢代酸离子载体四氢松黄素的假定生物合成前体描述。
• Sanglifehrin−Cyclophilin Interaction:  Degradation Work, Synthetic Macrocyclic Analogues, X-ray Crystal Structure, and Binding Data
  作者：Richard Sedrani、Jörg Kallen、Luisa M. Martin Cabrejas、Charles D. Papageorgiou、Francesco Senia、Stefan Rohrbach、Dieter Wagner、Binh Thai、Anne-Marie Jutzi Eme、Julien France、Lukas Oberer、Grety Rihs、Gerhard Zenke、Jürgen Wagner

  DOI：10.1021/ja021327y

  日期：2003.4.1

  Sanglifehrin A (SFA) is a novel immunosuppressive natural product isolated from Streptomyces sp. A92-308110. SFA has a very strong affinity for cyclophilin A (IC50 = 6.9 +/- 0.9 nM) but is structurally different from cyclosporin A (CsA) and exerts its immunosuppressive activity via a novel mechanism. SFA has a complex molecular structure consisting of a 22-membered macrocycle, bearing in position 23 a nine-carbon tether terminated by a highly substituted spirobicyclic moiety. Selective oxidative cleavage of the C-26=C-27 exocyclic double bond affords the spirolactam containing fragment 1 and macrolide 2. The affinity of 2 for cyclophilin (IC50 = 29 +/- 2.1 nM) is essentially identical to SFA, which indicates that the interaction between SFA and cyclophilin A is mediated exclusively by the macrocyclic portion of the molecule. This observation was confirmed by the X-ray crystal structure resolved at 2.1 Angstrom of cyclophilin A complexed to macrolide 16, a close analogue of 2. The X-ray crystal structure showed that macrolide 16 binds to the same deep hydrophobic pocket of cyclophilin A as CsA. Additional valuable details of the structure-activity relationship were obtained by two different chemical approaches: (1) degradation work on macrolide 2 or (2) synthesis of a library of macrolide analogues using the ring-closing metathesis reaction as the key step. Altogether, it appears that the complex macrocyclic fragment of SFA is a highly optimized combination of multiple functionalities including an (E,E)-diene, a short polypropionate fragment, and an unusual tripeptide unit, which together provide an extremely strong affinity for cyclophilin A.
• RICH, DANIEL H.;SUN, CHONG-QING;GUILLAUME, DOMINIQUE;DUNLAP, BRIAN;EVANS,+, J. MED. CHEM., 32,(1989) N, C. 1982-1987
  作者：RICH, DANIEL H.、SUN, CHONG-QING、GUILLAUME, DOMINIQUE、DUNLAP, BRIAN、EVANS,+

  DOI：——

  日期：——
• Total synthesis of a potent immunosuppressant pironetin
  作者：Mukund K Gurjar、John T Henri、D Subhas Bose、A V Rama Rao

  DOI：10.1016/0040-4039(96)01413-x

  日期：1996.9

  Total synthesis of PA-48153C Pironetin — a potent immunosuppressant is described.

  PA-48153C吡咯丁酮的全合成-一种有效的免疫抑制剂。