asiminocin | 174693-31-3

• 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: asiminocin
• 英文别名: (2S)-4-[(13R)-13-[(2R,5R)-5-[(2R,5R)-5-[(1R,7S)-1,7-dihydroxyundecyl]oxolan-2-yl]oxolan-2-yl]-13-hydroxytridecyl]-2-methyl-2H-furan-5-one
• CAS: 174693-31-3
• 化学式: C₃₇H₆₆O₇
• 分子量: 622.927
• InChiKey: GANIEPAALYJCMH-WGCJABNLSA-N

物化性质

• 沸点：
  757.6±40.0 °C(Predicted)
• 密度：
  1.054±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  9.3
• 重原子数：
  44
• 可旋转键数：
  25
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  105
• 氢给体数：
  3
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  N,O-双三甲硅基乙酰胺 、 asiminocin 在 吡啶 作用下， 反应 0.5h， 生成 (S)-3-{(R)-13-[(2R,5R,2'R,5'R)-5'-((1R,7S)-1,7-Bis-trimethylsilanyloxy-undecyl)-octahydro-[2,2']bifuranyl-5-yl]-13-trimethylsilanyloxy-tridecyl}-5-methyl-5H-furan-2-one
  参考文献：
  名称：

  The absolute configuration of adjacent bis-THF acetogenins and asiminocin, a novel highly potent asimicin isomer from Asimina triloba

  摘要：

  A novel acetogenin, asiminocin (1), was isolated by activity-directed fractionation from the stem bark of the paw paw tree, Asimina triloba. By spectral and chemical methods, 1 was identified as (30S)-hydroxy-4-deoxyasimicin. The absolute configuration of 1, along with those of previously reported acetogenins asimin, asiminacin, bullatin, (30S)-bullanin, and (30R) bullanin, was determined by Mosher ester methodology. Compound 1 was highly inhibitory to three human solid tumor cell lines with over a billion times the potency of adriamycin.

  DOI：

  10.1016/0968-0896(95)00155-7
• 作为产物：
  描述：

  反式-2-戊烯醛 在 Rh/Al₂O₃ 吡啶 、 chromium dichloride 、 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 、 草酰氯 、 四丁基氟化铵 、 氢气 、 sodium acetate 、 4-甲基苯磺酸吡啶 、 三乙基硼氢化锂 、 二甲基亚砜 、 二乙胺 、 三乙胺 、 对甲苯磺酰肼 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 乙二醇二甲醚 、 乙醇 、 二氯甲烷 、 乙酸乙酯 为溶剂， 反应 103.5h， 生成 asiminocin
  参考文献：
  名称：

  Total Synthesis of the Annonaceous Acetogenins Asiminocin and Asiminecin by a Bidirectional Approach

  摘要：

  A total synthesis of the Annonaceous acetogenins asiminocin and asiminecin is described. The approach is bidirectional starting from the (S,S)-tartrate derived dialdehyde 7 and the (R)-alpha-OSEM stannane 6. Addition of 6 to 7 in the presence of InCl3 afforded the bis-adduct, anti-diol 8. The derived tosylate 9 was converted to the bis-tetrahydrofuran core unit 10 upon treatment with TBAF. Selective silylation of one of the two equivalent terminal diol groupings led to the OTBS ether alcohol 11. Oxidation to aldehyde 12 and then InCl3-promoted addition of the (S)-allylic stannane 14 gave the anti adduct 15. Removal of the OH group by reduction of the tosylate 16 with LiBEt3H yielded the SEM ether 17. Hydrogenation of the three double bonds of 17 followed by cleavage of the terminal silyl ether and oxidation afforded aldehyde 20. Conversion to the vinylic iodide 21 followed by Pd(0)-catalyzed coupling with the (S)-alkynyl butenolide 24 gave the asiminocin derivative 25. Selective hydrogenation of the enyne moiety with diimide and cleavage of the SEM protecting groups completed the synthesis of asiminocin (27). Asiminecin (41) was prepared starting from aldehyde 12 and the OTBS allylic stannane 28. Addition of the latter to the former in the presence of InCl3 afforded the anti adduct 29 which was protected as the SEM ether 30. Hydrogenation followed by OTBS cleavage with TBAF and selective silylation of the primary alcohol with TBSCl and Et3N-DMAP led to the secondary alcohol 33. Tosylation and hydrogenolysis with LiEt3BH removed the C30 OTs group affording the SEM ether 35. The remaining steps were carried out along the lines described for asiminocin via the vinyl iodide 38 which was coupled with acetylenic butenolide 24 to afford enyne 39. Selective reduction with diimide and SEM cleavage completed the synthesis.

  DOI：

  10.1021/jo970424k

文献信息

• A Modular Synthesis of Annonaceous Acetogenins
  作者：James A. Marshall、Arnaud Piettre、Mikell A. Paige、Frederick Valeriote

  DOI：10.1021/jo026433x

  日期：2003.3.1

  A-G, is described. The approach employs a central core aldehyde segment, C, to which are appended an aliphatic terminus, A or B, a spacer subunit, D or E, and a butenolide terminus, F or G. Coupling of the A, B, D, and E segments to the core aldehyde unit is effected by highly diastereoselective additions of enantiopure allylic indium or tin reagents. The butenolide termini are attached to the ACD

  描述了通过七个基本亚基AG的模块化方法，合成了四种无丙酮产乙酸素，阿斯米诺星，阿斯米星，阿斯米星和布兰宁。该方法采用中央核心醛链段C，脂肪链末端A或B，间隔物亚基D或E和丁烯内酯末端F或G附加在中央醛基链段上。A，B，D和C的偶联通过对映体纯的烯丙基铟或锡试剂的高度非对映选择性添加来实现核心醛单元的E链段。丁烯内酯末端通过Sonogashira偶联连接到ACD，BCE或BCD中间体。核心，间隔子和末端亚基的设计使得可以制备任何C30，C10或C4天然产乙酸原素或其立体异构体。发现上述四种乙酸原素对H-116人结肠癌细胞的IC50值在10（-3）至10（-4）microM范围内。IC90的活动约为。10（-3）microM的asimicin和asimin，但仅0.1-1 microM的Bullanin和asiminocin。
• Total Synthesis of the Annonaceous Acetogenins Asiminocin and Asiminecin by a Bidirectional Approach
  作者：James A. Marshall、Minzhang Chen

  DOI：10.1021/jo970424k

  日期：1997.8.1

  A total synthesis of the Annonaceous acetogenins asiminocin and asiminecin is described. The approach is bidirectional starting from the (S,S)-tartrate derived dialdehyde 7 and the (R)-alpha-OSEM stannane 6. Addition of 6 to 7 in the presence of InCl3 afforded the bis-adduct, anti-diol 8. The derived tosylate 9 was converted to the bis-tetrahydrofuran core unit 10 upon treatment with TBAF. Selective silylation of one of the two equivalent terminal diol groupings led to the OTBS ether alcohol 11. Oxidation to aldehyde 12 and then InCl3-promoted addition of the (S)-allylic stannane 14 gave the anti adduct 15. Removal of the OH group by reduction of the tosylate 16 with LiBEt3H yielded the SEM ether 17. Hydrogenation of the three double bonds of 17 followed by cleavage of the terminal silyl ether and oxidation afforded aldehyde 20. Conversion to the vinylic iodide 21 followed by Pd(0)-catalyzed coupling with the (S)-alkynyl butenolide 24 gave the asiminocin derivative 25. Selective hydrogenation of the enyne moiety with diimide and cleavage of the SEM protecting groups completed the synthesis of asiminocin (27). Asiminecin (41) was prepared starting from aldehyde 12 and the OTBS allylic stannane 28. Addition of the latter to the former in the presence of InCl3 afforded the anti adduct 29 which was protected as the SEM ether 30. Hydrogenation followed by OTBS cleavage with TBAF and selective silylation of the primary alcohol with TBSCl and Et3N-DMAP led to the secondary alcohol 33. Tosylation and hydrogenolysis with LiEt3BH removed the C30 OTs group affording the SEM ether 35. The remaining steps were carried out along the lines described for asiminocin via the vinyl iodide 38 which was coupled with acetylenic butenolide 24 to afford enyne 39. Selective reduction with diimide and SEM cleavage completed the synthesis.
• The absolute configuration of adjacent bis-THF acetogenins and asiminocin, a novel highly potent asimicin isomer from Asimina triloba
  作者：Geng-Xian Zhao、Jin-Feng Chao、Lu Zeng、Matthew J. Rieser、Jerry L. McLaughlin

  DOI：10.1016/0968-0896(95)00155-7

  日期：1996.1

  A novel acetogenin, asiminocin (1), was isolated by activity-directed fractionation from the stem bark of the paw paw tree, Asimina triloba. By spectral and chemical methods, 1 was identified as (30S)-hydroxy-4-deoxyasimicin. The absolute configuration of 1, along with those of previously reported acetogenins asimin, asiminacin, bullatin, (30S)-bullanin, and (30R) bullanin, was determined by Mosher ester methodology. Compound 1 was highly inhibitory to three human solid tumor cell lines with over a billion times the potency of adriamycin.