N-benzyl-N-[(S)-[(4S,5S)-2,2-dimethyl-5-(phenylmethoxymethyl)-1,3-dioxolan-4-yl]-(furan-2-yl)methyl]hydroxylamine | 152390-97-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: N-benzyl-N-[(S)-[(4S,5S)-2,2-dimethyl-5-(phenylmethoxymethyl)-1,3-dioxolan-4-yl]-(furan-2-yl)methyl]hydroxylamine
• CAS: 152390-97-1
• 化学式: C₂₅H₂₉NO₅
• 分子量: 423.509
• InChiKey: TXZYUIYBSRZSFH-RBZQAINGSA-N

物化性质

• 沸点：
  549.9±50.0 °C(predicted)
• 密度：
  1.184±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  31
• 可旋转键数：
  9
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  64.3
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  N-benzyl-N-[(S)-[(4S,5S)-2,2-dimethyl-5-(phenylmethoxymethyl)-1,3-dioxolan-4-yl]-(furan-2-yl)methyl]hydroxylamine 在 ruthenium trichloride 、 sodium periodate 、 titanium(III) chloride 、 氨 、 sodium 、 silica gel 、 N,N-二异丙基乙胺 、 N,N'-二环己基碳二亚胺 、 三氟乙酸 作用下， 以 1,4-二氧六环 、 吡啶 、 甲醇 、 四氯化碳 、 乙醚 、 氨 、 水 、 二甲基亚砜 、 乙酸乙酯 、 乙腈 为溶剂， 反应 77.58h， 生成 (S)-((2S,3S,4S)-2-Amino-5-carbamoyloxy-3,4-dihydroxy-pentanoylamino)-[(2R,3S,4R,5R)-3,4-dihydroxy-5-(6-methyl-2,4-dioxo-3,4-dihydro-2H-pyrimidin-1-yl)-tetrahydro-furan-2-yl]-acetic acid
  参考文献：
  名称：

  Applications of Sugar Nitrones in Synthesis:  The Total Synthesis of (+)-Polyoxin J¹

  摘要：

  A convergent synthesis of the peptidyl nucleoside antibiotic (inhibitor of chitin biosynthesis) polyoxin J (2) by coupling of 5-O-carbamoyl polyoxamic acid (3) and thymine polyoxin C (4) is described. These compounds were prepared by chain elongation and amination of sugar-derived aldehydes employing their nitrones as iminium derivatives and the furan ring as a masked carboxyl. Thus, the stereoselective addition of 2-lithiofuran to the L-threose derived N-benzyl nitrone 5 followed by reduction of the resulting hydroxylamine to amine, carbamoylation of the free hydroxy group, and oxidative cleavage of the furan ring to the carboxylate group gave a protected derivative of 3 (30%). The same method was followed for the synthesis of the ribofuranosyl alpha-amino acid nucleoside 4 (12.6%) starting from the D-ribose derived nitrone 6. The final coupling was performed by the N-hydroxysuccinimide active ester method in DMSO with the Hunig base (i-Pr2EtNH) using a derivative of 3 and unprotected 4.

  DOI：

  10.1021/jo9702913
• 作为产物：
  描述：

  (4S,5R)-4-benzyloxymethyl-2,2-dimethyl-1,3-dioxolane-5-carboxaldehyde 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 12.25h， 生成 N-benzyl-N-[(S)-[(4S,5S)-2,2-dimethyl-5-(phenylmethoxymethyl)-1,3-dioxolan-4-yl]-(furan-2-yl)methyl]hydroxylamine
  参考文献：
  名称：

  通过在α-烷氧基硝酮中添加2-硫代呋喃和N-甲基-2-硫代咪唑中的氯化二乙基铝进行立体控制。5- O-氨基甲酰基聚乙酰胺酸的全合成。

  摘要：

  在衍生自D-甘油醛丙酮化物的硝酮2中添加标题金属化杂环1会导致相应的正加合物作为主要产物（ds 88–96％），而在Et 2 AlCl存在下的反应会导致反异构体（ ds 79–95％）；描述了通过硝基-呋喃加合物由4-O-苄基-2,3-O-异亚丙基-L-苏糖合成5-O-氨基甲酰基聚乙酰胺酸

  DOI：

  10.1016/s0040-4039(00)73939-6

文献信息

• Addition of 2-Lithiofuran to Chiral α-Alkoxy Nitrones; a Stereoselective Approach to α-Epimeric β-Alkoxy-α-amino Acids
  作者：A. Dondoni、F. Junquera、F. L. Merchan、P. Merino、T. Tejero

  DOI：10.1055/s-1994-25712

  日期：——

  The addition of 2-lithiofuran (1) to the N-benzyl nitrones 2a-d, derived from chiral α-alkoxy aldehydes, affords β-alkoxy-α-hydroxyamino-2-alkylfurans in good yields and with syn selectivity. Conversely, the reaction with the same nitrones precomplexed with diethylaluminum chloride leads to the same adducts but with anti selectivity. Three pairs of epimeric hydroxylamines are subjected to reductive N-dehydroxylation with titanium(III) chloride and then to furyl-carboxylic acid conversion with ruthenium tetroxide to give the corresponding α-epimeric β-alkoxy-α-amino acids.

  将 2-锂硫呋喃 (1) 添加到衍生自手性 α-烷氧基醛的 N-苄基硝酮 2a-d 中，以良好的产率和顺式选择性提供 β-烷氧基-α-羟基氨基-2-烷基呋喃。相反，与与二乙基氯化铝预络合的相同硝酮的反应产生相同的加合物，但具有反选择性。三对差向异构羟胺用氯化钛(III) 进行还原性N-脱羟基，然后用四氧化钌进行呋喃基-羧酸转化，得到相应的α-差向异构β-烷氧基-α-氨基酸。
• Applications of Sugar Nitrones in Synthesis:  The Total Synthesis of (+)-Polyoxin J¹
  作者：Alessandro Dondoni、Santiago Franco、Federico Junquera、Francisco L. Merchán、Pedro Merino、Tomás Tejero

  DOI：10.1021/jo9702913

  日期：1997.8.1

  A convergent synthesis of the peptidyl nucleoside antibiotic (inhibitor of chitin biosynthesis) polyoxin J (2) by coupling of 5-O-carbamoyl polyoxamic acid (3) and thymine polyoxin C (4) is described. These compounds were prepared by chain elongation and amination of sugar-derived aldehydes employing their nitrones as iminium derivatives and the furan ring as a masked carboxyl. Thus, the stereoselective addition of 2-lithiofuran to the L-threose derived N-benzyl nitrone 5 followed by reduction of the resulting hydroxylamine to amine, carbamoylation of the free hydroxy group, and oxidative cleavage of the furan ring to the carboxylate group gave a protected derivative of 3 (30%). The same method was followed for the synthesis of the ribofuranosyl alpha-amino acid nucleoside 4 (12.6%) starting from the D-ribose derived nitrone 6. The final coupling was performed by the N-hydroxysuccinimide active ester method in DMSO with the Hunig base (i-Pr2EtNH) using a derivative of 3 and unprotected 4.
• Stereocontrol by diethylaluminum chloride in the addition of 2-lithiofuran and N-methyl-2-lithioimidazole to α-alkoxy nitrones. Total synthesis of 5-O-carbamoylpolyoxamic acid.
  作者：Alessandro Dondoni、Santiago Franco、Francisco Luis Merchán、Pedro Merino、Tomás Tejero

  DOI：10.1016/s0040-4039(00)73939-6

  日期：1993.1

  derived from D-glyceraldehyde acetonide leads to the corresponding syn-adducts as major products (ds 88–96 %) while the reaction in the presence of Et2AlCl leads to anti isomers (ds 79–95 %); the synthesis of 5-O-carbamoylpolyoxamic acid from 4-O-benzyl-2,3-O-isopropylidene-L-threose via the nitrone-furan adduct is described

  在衍生自D-甘油醛丙酮化物的硝酮2中添加标题金属化杂环1会导致相应的正加合物作为主要产物（ds 88–96％），而在Et 2 AlCl存在下的反应会导致反异构体（ ds 79–95％）；描述了通过硝基-呋喃加合物由4-O-苄基-2,3-O-异亚丙基-L-苏糖合成5-O-氨基甲酰基聚乙酰胺酸