(6S)-N-Acetyl-N-benzyl-6-amino-6,7-Dideoxy-1,2:3,4-di-O-isopropylidene-α-D-galacto-octodialdo-1,5-pyranose | 132163-95-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氧吡喃
• 英文名称: (6S)-N-Acetyl-N-benzyl-6-amino-6,7-Dideoxy-1,2:3,4-di-O-isopropylidene-α-D-galacto-octodialdo-1,5-pyranose
• 英文别名: 6-(N-benzyl)acetamido-6,7-dideoxy-1,2:3,4-di-O-isopropylidene-L-glycero-α-D-galacto-octodialo-1,5-pyranose；N-benzyl-N-[(1S)-3-oxo-1-[(1S,2R,6R,8R,9S)-4,4,11,11-tetramethyl-3,5,7,10,12-pentaoxatricyclo[7.3.0.02,6]dodecan-8-yl]propyl]acetamide
• CAS: 132163-95-2
• 化学式: C₂₃H₃₁NO₇
• 分子量: 433.502
• InChiKey: MEGUSBPAWSALBB-NXMWLWCLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  31
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  83.5
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  (6S)-N-Acetyl-N-benzyl-6-amino-6,7-Dideoxy-1,2:3,4-di-O-isopropylidene-α-D-galacto-octodialdo-1,5-pyranose 在 sodium tetrahydroborate 作用下， 以 甲醇 为溶剂， 以80%的产率得到(6S)-N-Acetyl-N-benzyl-6-amino-6,7-Dideoxy-1,2:3,4-di-O-isopropylidene-α-D-galacto-octulo-1,5-pyranose
  参考文献：
  名称：

  氮亲核试剂向2-烯基正甲基碘化偶氮碘的区域和立体选择性共轭加成。d-3-表柔红胺和一些林可胺类似物的合成

  摘要：

  描述了醛的二碳同系胺化技术。关键步骤涉及将迈克尔亲子型氮原子（苄胺，三甲基甲硅烷基叠氮化物，邻苯二甲酰亚胺钾）迈克尔型加成到2-烯基N-甲基噻唑鎓盐中，该盐是通过将醛与ane烷（1）进行烯化反应而得到的，并进行噻唑-甲酰基解嵌段反应。加入benzylaminine的从D-甘油的丙酮衍生的噻唑鎓盐与良好的水平发生顺-diastereoselectivity（DS，85-90％）与改性Felkin-映模型的协议。这项技术用于从4-脱氧D-苏糖到D-3-表位-柔红胺和从α-D-十二烷基四吡喃糖得到的一些林可胺类似物的短合成路线中。

  DOI：

  10.1016/s0040-4020(01)87939-4
• 作为产物：
  描述：

  (Z)-N-benzyl-(1,2:3,4-di-O-isopropylidene-α-D-galactopyranos-6-ylidene)amine N-oxide 在 碳酸氢钠 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 24.75h， 生成 (6S)-N-Acetyl-N-benzyl-6-amino-6,7-Dideoxy-1,2:3,4-di-O-isopropylidene-α-D-galacto-octodialdo-1,5-pyranose
  参考文献：
  名称：

  Higher glycosamino acid precursors: C7 and C8 aminodialdoses via regio- and stereoselective [3+2] cycloaddition of vinyl trimethylsilane to C-glycosyl nitrones

  摘要：

  Protected C-7 and C-8 aminodialdoses were prepared stereoselectively from readily available C-5 and C-6 monosaccharide N-benzyl nitrones, by regio- and diastereoselective 1,3-dipolar cycloaddition reactions with vinyl trimethylsilane, followed by acetyl chloride-mediated cleavage of the 5-(trimethylsilyl)isoxazolidine formed. The cycloaddition reaction took place in moderate to good global yields (67-74%); estimation of diastereoselectivities from isolated yields showed total endo preference for the reaction of the D-galacto configured nitrone and high endo preference for the D-ribo analogue, but exo preference for the D-Xylo configured substrate. Attack on the re face of the nitrone was predominant in all cases. The absolute configuration of one of the protected 3-(alpha-D-galacto-pentopyranos-5-yl)isoxazolidine products was assigned by X-ray crystallographic analysis, allowing correlation of the configuration at the new stereogenic centre in the corresponding aminodialdose. For non-crystalline isoxazolidines, configurations were assigned on the basis of NOESY experiments and/or chemical correlation. Combined yields of aminodialdoses coming from isoxazolidines having identical configuration at C(3) sometimes reached high values (up to 90%). These compounds are precursors of higher-chain glycosamino acids. (C) 2002 Published by Elsevier Science Ltd.

  DOI：

  10.1016/s0957-4166(02)00543-8

文献信息

• Higher glycosamino acid precursors: C7 and C8 aminodialdoses via regio- and stereoselective [3+2] cycloaddition of vinyl trimethylsilane to C-glycosyl nitrones
  作者：Pastora Borrachero、Francisca Cabrera-Escribano、Ma Jesús Diánez、Ma Dolores Estrada、Manuel Gómez-Guillén、Amparo López Castro、Simeón Pérez-Garrido、Ma Isabel Torres

  DOI：10.1016/s0957-4166(02)00543-8

  日期：2002.9

  Protected C-7 and C-8 aminodialdoses were prepared stereoselectively from readily available C-5 and C-6 monosaccharide N-benzyl nitrones, by regio- and diastereoselective 1,3-dipolar cycloaddition reactions with vinyl trimethylsilane, followed by acetyl chloride-mediated cleavage of the 5-(trimethylsilyl)isoxazolidine formed. The cycloaddition reaction took place in moderate to good global yields (67-74%); estimation of diastereoselectivities from isolated yields showed total endo preference for the reaction of the D-galacto configured nitrone and high endo preference for the D-ribo analogue, but exo preference for the D-Xylo configured substrate. Attack on the re face of the nitrone was predominant in all cases. The absolute configuration of one of the protected 3-(alpha-D-galacto-pentopyranos-5-yl)isoxazolidine products was assigned by X-ray crystallographic analysis, allowing correlation of the configuration at the new stereogenic centre in the corresponding aminodialdose. For non-crystalline isoxazolidines, configurations were assigned on the basis of NOESY experiments and/or chemical correlation. Combined yields of aminodialdoses coming from isoxazolidines having identical configuration at C(3) sometimes reached high values (up to 90%). These compounds are precursors of higher-chain glycosamino acids. (C) 2002 Published by Elsevier Science Ltd.
• Regio- and stereoselective conjugate addition of nitrogen nucleophiles to 2-alkenyl n-methylthiazolium iodides. synthesis of d-3-epi-daunosamine and some lincosamine analogues
  作者：Alessandro Dondoni、Giancarlo Fantin、Marco Fogagnolo、Pedro Merino

  DOI：10.1016/s0040-4020(01)87939-4

  日期：1990.1

  on technology of aldehydes is described. Key steps involve the Michael-type addition of a nitrogen nucleophile (benzylamine, trimethylsilylazide, potassium phtalimide) to a 2-alkenyl N-methylthiazolium salt obtained by olefination of the aldehyde with the phosphorane (1), and the thiazole-to-formyl deblocking. The addition of benzylaminine to the thiazolium salt derived from the acetonide of D- glyceraldehyde

  描述了醛的二碳同系胺化技术。关键步骤涉及将迈克尔亲子型氮原子（苄胺，三甲基甲硅烷基叠氮化物，邻苯二甲酰亚胺钾）迈克尔型加成到2-烯基N-甲基噻唑鎓盐中，该盐是通过将醛与ane烷（1）进行烯化反应而得到的，并进行噻唑-甲酰基解嵌段反应。加入benzylaminine的从D-甘油的丙酮衍生的噻唑鎓盐与良好的水平发生顺-diastereoselectivity（DS，85-90％）与改性Felkin-映模型的协议。这项技术用于从4-脱氧D-苏糖到D-3-表位-柔红胺和从α-D-十二烷基四吡喃糖得到的一些林可胺类似物的短合成路线中。