(2S,3S,4E)-2--1-O-(tert-butyldimethylsilyl)-4-hexene-1,3-diol | 157037-45-1

• 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: (2S,3S,4E)-2--1-O-(tert-butyldimethylsilyl)-4-hexene-1,3-diol
• 英文别名: (E,2S,3S)-2-(benzhydrylideneamino)-1-[tert-butyl(dimethyl)silyl]oxyhex-4-en-3-ol
• CAS: 157037-45-1
• 化学式: C₂₅H₃₅NO₂Si
• 分子量: 409.644
• InChiKey: UREZJRPGTRBSSZ-YXPYFTIYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.85
• 重原子数：
  29
• 可旋转键数：
  9
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  41.8
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2S,3S,4E)-2--1-O-(tert-butyldimethylsilyl)-4-hexene-1,3-diol 在 吡啶 、 4-二甲氨基吡啶 、 potassium dioxotetrahydroxoosmate(VI) 、 氢氟酸 、 sodium cyanoborohydride 、 potassium carbonate 、 溶剂黄146 、 potassium hexacyanoferrate(III) 作用下， 以 水 、 乙腈 、 叔丁醇 为溶剂， 反应 28.17h， 生成 (2S,3R,4S,5R)-3,4,5-Triacetoxy-2-hexan-1-ol
  参考文献：
  名称：

  An Enantioselective Synthesis of N-Methylfucosamine via Tandem C-C/C-O Bond Formation

  摘要：

  Optically pure D-(+)-N-methylfucosamine (8) has been synthesized from a TBDMS-protected methyl L-serinate benzophenone Schiff base (O'Donnell's Schiff base, 1) in seven steps in 13% overall yield. Efficient construction-of the requisite amino triol acetate 3a with the proper stereochemical configuration is accomplished in two steps with a chelation-controlled reduction-alkylation reaction using \Bu(2)AlH.Al-iBu(3)/E-LiCH=CHCH3, followed by oxidation with OsO4. Conversion of the Schiff base to the N-benzhydryl protecting group and methylation (Eschweiler-Clark) is accomplished in one pot with NaCNBH3 in ti;e presence of H2C=O. Deprotection and oxidation of the primary alcohol, followed by deacetylation with KCN, provided the desired product 8.

  DOI：

  10.1021/jo00095a039
• 作为产物：
  描述：

  (E)-propenyl lithium 、 methyl O-tert-butyldimethylsilyl-N-(diphenylmethylene)-L-serinate 在 i-Bu₂AlH*i-Bu₃Al 作用下， 以 甲苯 为溶剂， 以70%的产率得到(2S,3S,4E)-2--1-O-(tert-butyldimethylsilyl)-4-hexene-1,3-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.
• An Enantioselective Synthesis of N-Methylfucosamine via Tandem C-C/C-O Bond Formation
  作者：Dalibor Sames、Robin Polt

  DOI：10.1021/jo00095a039

  日期：1994.8

  Optically pure D-(+)-N-methylfucosamine (8) has been synthesized from a TBDMS-protected methyl L-serinate benzophenone Schiff base (O'Donnell's Schiff base, 1) in seven steps in 13% overall yield. Efficient construction-of the requisite amino triol acetate 3a with the proper stereochemical configuration is accomplished in two steps with a chelation-controlled reduction-alkylation reaction using \Bu(2)AlH.Al-iBu(3)/E-LiCH=CHCH3, followed by oxidation with OsO4. Conversion of the Schiff base to the N-benzhydryl protecting group and methylation (Eschweiler-Clark) is accomplished in one pot with NaCNBH3 in ti;e presence of H2C=O. Deprotection and oxidation of the primary alcohol, followed by deacetylation with KCN, provided the desired product 8.