(4S,5S,2Z)-5-amino-1-O-tert-butyldimethylsilyl-N-diphenylmethylene-4-O-pivaloyl-2-hexen-1,4-diol

• 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: (4S,5S,2Z)-5-amino-1-O-tert-butyldimethylsilyl-N-diphenylmethylene-4-O-pivaloyl-2-hexen-1,4-diol
• 英文别名: [(Z,2S,3S)-2-(benzhydrylideneamino)-6-[tert-butyl(dimethyl)silyl]oxyhex-4-en-3-yl] 2,2-dimethylpropanoate
• 化学式: C₃₀H₄₃NO₃Si
• 分子量: 493.762
• InChiKey: APJZQVIXQMNPID-ZAZOFKEJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.45
• 重原子数：
  35
• 可旋转键数：
  12
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  47.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (4S,5S,2Z)-5-amino-1-O-tert-butyldimethylsilyl-N-diphenylmethylene-4-O-pivaloyl-2-hexen-1,4-diol 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 生成 2,2-Dimethyl-propionic acid (Z)-(S)-1-[(S)-1-(benzhydrylidene-amino)-ethyl]-4-hydroxy-but-2-enyl ester
  参考文献：
  名称：

  Glycosidase Inhibitors:  Synthesis of Enantiomerically Pure Aza-Sugars from Schiff Base Amino Esters via Tandem Reduction-Alkenylation and Osmylation

  摘要：

  Nitrogen-in-the-ring "aza-sugars" have been synthesized in enantiomerically pure form from the amino acid L-alanine in excellent overall yield. The O'Donnell's Schiff base of L-alanine methyl ester 9a was converted to ate-sugar L-fuco-1-deoxy-nojirimycin, 18, and to the epimer L-gulo-1-deoxy-nojirimycin, 20, in eight steps. The overall yields were 20 and 29%, respectively. The methodology for the efficient generation of silyl- and benzyl-protected (E)-3-lithio-2-propen-1-ols, and the use of these alkenyllithiums with iBu(5)Al(2)H as nucleophiles in the three-selective tandem reduction-alkenylation of the Schiff base esters is described. Osmium-catalyzed cis-oxygenation of the resulting olefin products was selective for the galacto (fuco) amino polyols in all cases for the acyclic olefins, and was gulo-selective for the cyclic D-4,5-dihydropyridine pivalate, 17c. TEMPO-NaOCl was selective for oxidation of the primary position of the acyclic Schiff bases, and allowed for minimal protection/deprotection of the intermediates. The resulting N-benzhydryl heterocycles were easily deprotected with H-2-Pd at atmospheric pressure.

  DOI：

  10.1021/jo9820115
• 作为产物：
  描述：

  叔丁基二甲基(2-丙炔氧基)硅烷 在 吡啶 、 4-二甲氨基吡啶 、 偶氮二异丁腈 、 叔丁基锂 、 三正丁基氢锡 作用下， 以 正己烷 、 正戊烷 为溶剂， 反应 16.5h， 生成 (4S,5S,2Z)-5-amino-1-O-tert-butyldimethylsilyl-N-diphenylmethylene-4-O-pivaloyl-2-hexen-1,4-diol
  参考文献：
  名称：

  Glycosidase Inhibitors:  Synthesis of Enantiomerically Pure Aza-Sugars from Schiff Base Amino Esters via Tandem Reduction-Alkenylation and Osmylation

  摘要：

  Nitrogen-in-the-ring "aza-sugars" have been synthesized in enantiomerically pure form from the amino acid L-alanine in excellent overall yield. The O'Donnell's Schiff base of L-alanine methyl ester 9a was converted to ate-sugar L-fuco-1-deoxy-nojirimycin, 18, and to the epimer L-gulo-1-deoxy-nojirimycin, 20, in eight steps. The overall yields were 20 and 29%, respectively. The methodology for the efficient generation of silyl- and benzyl-protected (E)-3-lithio-2-propen-1-ols, and the use of these alkenyllithiums with iBu(5)Al(2)H as nucleophiles in the three-selective tandem reduction-alkenylation of the Schiff base esters is described. Osmium-catalyzed cis-oxygenation of the resulting olefin products was selective for the galacto (fuco) amino polyols in all cases for the acyclic olefins, and was gulo-selective for the cyclic D-4,5-dihydropyridine pivalate, 17c. TEMPO-NaOCl was selective for oxidation of the primary position of the acyclic Schiff bases, and allowed for minimal protection/deprotection of the intermediates. The resulting N-benzhydryl heterocycles were easily deprotected with H-2-Pd at atmospheric pressure.

  DOI：

  10.1021/jo9820115

文献信息

• Glycosidase Inhibitors:  Synthesis of Enantiomerically Pure Aza-Sugars from Schiff Base Amino Esters via Tandem Reduction-Alkenylation and Osmylation
  作者：Robin Polt、Dalibor Sames、Jason Chruma

  DOI：10.1021/jo9820115

  日期：1999.8.1

  Nitrogen-in-the-ring "aza-sugars" have been synthesized in enantiomerically pure form from the amino acid L-alanine in excellent overall yield. The O'Donnell's Schiff base of L-alanine methyl ester 9a was converted to ate-sugar L-fuco-1-deoxy-nojirimycin, 18, and to the epimer L-gulo-1-deoxy-nojirimycin, 20, in eight steps. The overall yields were 20 and 29%, respectively. The methodology for the efficient generation of silyl- and benzyl-protected (E)-3-lithio-2-propen-1-ols, and the use of these alkenyllithiums with iBu(5)Al(2)H as nucleophiles in the three-selective tandem reduction-alkenylation of the Schiff base esters is described. Osmium-catalyzed cis-oxygenation of the resulting olefin products was selective for the galacto (fuco) amino polyols in all cases for the acyclic olefins, and was gulo-selective for the cyclic D-4,5-dihydropyridine pivalate, 17c. TEMPO-NaOCl was selective for oxidation of the primary position of the acyclic Schiff bases, and allowed for minimal protection/deprotection of the intermediates. The resulting N-benzhydryl heterocycles were easily deprotected with H-2-Pd at atmospheric pressure.