(2S,3S)-1-Hydroxy-2-acetamido-3-methoxyhex-5-ene | 1054667-62-7

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (2S,3S)-1-Hydroxy-2-acetamido-3-methoxyhex-5-ene
• 英文别名: N-[(2S,3S)-1-hydroxy-3-methoxyhex-5-en-2-yl]acetamide
• CAS: 1054667-62-7
• 化学式: C₉H₁₇NO₃
• 分子量: 187.239
• InChiKey: OOTFVIBCBPDDCR-IUCAKERBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.1
• 重原子数：
  13
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  58.6
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2S,3S)-1-Hydroxy-2-acetamido-3-methoxyhex-5-ene 在 lithium aluminium tetrahydride 、 二甲基硫 、 臭氧 、 乙酰氯 作用下， 以 四氢呋喃 为溶剂， 反应 14.5h， 生成 methyl 2,4-dideoxy-4-(ethylamino)-3-O-methyl-α-L-threo-pentopyranoside
  参考文献：
  名称：

  Asymmetric Allylboration of 2-N,3-O-Isopropylidene-N-Boc-L-serinal: Diastereoselective Synthesis of the Calicheamicin .gamma.1I Amino Sugar

  摘要：

  Syntheses of the calicheamicin amino sugar 6 and its erythro diastereomer 7 have been completed by a sequence involving the asymmetric allylboration of N-Boc-serinal acetonide L-8 with the tartrate ester modified allylboronates (R,R)-9 and (S,S)-9, respectively. The reaction of(R,R)-9 and L-8 in toluene provides 14 with 89:11 selectivity, whereas the reaction of(S,S)-9 with L-8 in Et(2)O provides the diastereomer 15 with 90:10 selectivity. It is shown that the relatively modest diastereoselectivity of these double asymmetric reactions is compromised by the low enantiomeric purity of 8 (86-87% ee), and data are provided indicating that these reactions should be highly diastereoselective (greater than or equal to 95:5 in each case) if performed with enantiomerically pure aldehyde. The two diastereomeric homoallylic alcohols, 14 and 15, are easily elaborated into the targeted amino sugars 6 and 7 via the acetamide-substituted pyranosides 22 and 26. Methyl pyranosides 22a and 22e were shown to adopt preferentially the unexpected conformations B and D, with axial acetamide substituents, in nonpolar solvents, while the expected conformations A and C were strongly favored in d(6)-DMSO because of hydrogen bonding interactions with the solvent. The syntheses of 6 and 7 reported herein are expected to facilitate the design and synthesis of analogs of the calicheamicin aryl tetrasaccharide 3, which should prove useful in further analysis and applications of oligosaccharides as DNA binders.

  DOI：

  10.1021/jo00109a008
• 作为产物：
  描述：

  (2S,3S)-1-Acetoxy-2-acetamido-3-methoxyhex-5-ene 在 potassium carbonate 作用下， 以 甲醇 为溶剂， 反应 3.0h， 生成 (2S,3S)-1-Hydroxy-2-acetamido-3-methoxyhex-5-ene
  参考文献：
  名称：

  Asymmetric Allylboration of 2-N,3-O-Isopropylidene-N-Boc-L-serinal: Diastereoselective Synthesis of the Calicheamicin .gamma.1I Amino Sugar

  摘要：

  Syntheses of the calicheamicin amino sugar 6 and its erythro diastereomer 7 have been completed by a sequence involving the asymmetric allylboration of N-Boc-serinal acetonide L-8 with the tartrate ester modified allylboronates (R,R)-9 and (S,S)-9, respectively. The reaction of(R,R)-9 and L-8 in toluene provides 14 with 89:11 selectivity, whereas the reaction of(S,S)-9 with L-8 in Et(2)O provides the diastereomer 15 with 90:10 selectivity. It is shown that the relatively modest diastereoselectivity of these double asymmetric reactions is compromised by the low enantiomeric purity of 8 (86-87% ee), and data are provided indicating that these reactions should be highly diastereoselective (greater than or equal to 95:5 in each case) if performed with enantiomerically pure aldehyde. The two diastereomeric homoallylic alcohols, 14 and 15, are easily elaborated into the targeted amino sugars 6 and 7 via the acetamide-substituted pyranosides 22 and 26. Methyl pyranosides 22a and 22e were shown to adopt preferentially the unexpected conformations B and D, with axial acetamide substituents, in nonpolar solvents, while the expected conformations A and C were strongly favored in d(6)-DMSO because of hydrogen bonding interactions with the solvent. The syntheses of 6 and 7 reported herein are expected to facilitate the design and synthesis of analogs of the calicheamicin aryl tetrasaccharide 3, which should prove useful in further analysis and applications of oligosaccharides as DNA binders.

  DOI：

  10.1021/jo00109a008

文献信息

• Asymmetric Allylboration of 2-N,3-O-Isopropylidene-N-Boc-L-serinal: Diastereoselective Synthesis of the Calicheamicin .gamma.1I Amino Sugar
  作者：William R. Roush、J. A. Hunt

  DOI：10.1021/jo00109a008

  日期：1995.2

  Syntheses of the calicheamicin amino sugar 6 and its erythro diastereomer 7 have been completed by a sequence involving the asymmetric allylboration of N-Boc-serinal acetonide L-8 with the tartrate ester modified allylboronates (R,R)-9 and (S,S)-9, respectively. The reaction of(R,R)-9 and L-8 in toluene provides 14 with 89:11 selectivity, whereas the reaction of(S,S)-9 with L-8 in Et(2)O provides the diastereomer 15 with 90:10 selectivity. It is shown that the relatively modest diastereoselectivity of these double asymmetric reactions is compromised by the low enantiomeric purity of 8 (86-87% ee), and data are provided indicating that these reactions should be highly diastereoselective (greater than or equal to 95:5 in each case) if performed with enantiomerically pure aldehyde. The two diastereomeric homoallylic alcohols, 14 and 15, are easily elaborated into the targeted amino sugars 6 and 7 via the acetamide-substituted pyranosides 22 and 26. Methyl pyranosides 22a and 22e were shown to adopt preferentially the unexpected conformations B and D, with axial acetamide substituents, in nonpolar solvents, while the expected conformations A and C were strongly favored in d(6)-DMSO because of hydrogen bonding interactions with the solvent. The syntheses of 6 and 7 reported herein are expected to facilitate the design and synthesis of analogs of the calicheamicin aryl tetrasaccharide 3, which should prove useful in further analysis and applications of oligosaccharides as DNA binders.