Methyl 5-O-(tert-butyldiphenylsilyl)-2,6-dideoxy-β-D-erythro-hexofuranosid-3-ulose | 161606-80-0

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: Methyl 5-O-(tert-butyldiphenylsilyl)-2,6-dideoxy-β-D-erythro-hexofuranosid-3-ulose
• 英文别名: (2R,5R)-2-[(1R)-1-[tert-butyl(diphenyl)silyl]oxyethyl]-5-methoxyoxolan-3-one
• CAS: 161606-80-0
• 化学式: C₂₃H₃₀O₄Si
• 分子量: 398.574
• InChiKey: NQNGZCCMFAVWRU-ZPMCFJSWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.28
• 重原子数：
  28
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  Methyl 5-O-(tert-butyldiphenylsilyl)-2,6-dideoxy-β-D-erythro-hexofuranosid-3-ulose 在 甲基氯化镁 作用下， 以 四氢呋喃 为溶剂， 反应 0.17h， 以20%的产率得到Methyl 5-O-(tert-butyldiphenylsilyl)-2,6-dideoxy-3-C-methyl-β-D-arabino-hexofuranoside
  参考文献：
  名称：

  Stereoselectivity of Addition of Organometallic Reagents to Pentodialdo-1,4-furanoses: Synthesis of L-Axenose and D-Evermicose from a Common Intermediate

  摘要：

  The additions of organometallic reagents to two pentodialdo-1,4-furanosides (methyl 3-O-benzyl-2-deoxy-alpha-D-erythro-pentofuranoside and its beta-anomer) were carried out under a variety of experimental conditions. Methylmagnesium halides, methyllithium, methylcerium and the organotitanium reagent MeTi(OiPr)(3) were reacted with the pentodialdo-1,4-furanosides in an effort to determine if the stereoselectivity of addition to the formyl group is the result of chelation or nonchelation control and to determine the effect of anomeric configuration. The stereochemistry of the products was assigned by NMR methods and correlation with known compounds synthesized previously. The stereoselectivity of addition depends on the configuration at the anomeric center of the dialdose, with the beta-anomer giving mainly the product of a non-chelation-controlled addition and the beta-anomer giving the opposite stereoselectivity. The major product obtained from the beta-anomer was utilized as a key intermediate in the synthesis of two branched-chain carbohydrates, axenose and evermicose, found in antibiotics. Methylcerium additions are the most efficient method for introducing the branching methyl group in a 2-deoxyfuranosid-3-ulose.

  DOI：

  10.1021/jo00106a035
• 作为产物：
  描述：

  methyl 2-deoxy-3-O-benzyl-β-D-erythro-pentofuranoside 在 吡啶 、 咪唑 、 chromium(VI) oxide 、 氢氧化钾 、 N-溴代丁二酰亚胺(NBS) 、 草酰氯 、 乙酸酐 、 二甲基亚砜 、 三乙胺 、 calcium carbonate 作用下， 以 甲醇 、 四氯化碳 、 乙醚 、 二氯甲烷 为溶剂， 反应 36.25h， 生成 Methyl 5-O-(tert-butyldiphenylsilyl)-2,6-dideoxy-β-D-erythro-hexofuranosid-3-ulose
  参考文献：
  名称：

  Stereoselectivity of Addition of Organometallic Reagents to Pentodialdo-1,4-furanoses: Synthesis of L-Axenose and D-Evermicose from a Common Intermediate

  摘要：

  The additions of organometallic reagents to two pentodialdo-1,4-furanosides (methyl 3-O-benzyl-2-deoxy-alpha-D-erythro-pentofuranoside and its beta-anomer) were carried out under a variety of experimental conditions. Methylmagnesium halides, methyllithium, methylcerium and the organotitanium reagent MeTi(OiPr)(3) were reacted with the pentodialdo-1,4-furanosides in an effort to determine if the stereoselectivity of addition to the formyl group is the result of chelation or nonchelation control and to determine the effect of anomeric configuration. The stereochemistry of the products was assigned by NMR methods and correlation with known compounds synthesized previously. The stereoselectivity of addition depends on the configuration at the anomeric center of the dialdose, with the beta-anomer giving mainly the product of a non-chelation-controlled addition and the beta-anomer giving the opposite stereoselectivity. The major product obtained from the beta-anomer was utilized as a key intermediate in the synthesis of two branched-chain carbohydrates, axenose and evermicose, found in antibiotics. Methylcerium additions are the most efficient method for introducing the branching methyl group in a 2-deoxyfuranosid-3-ulose.

  DOI：

  10.1021/jo00106a035

文献信息

• Stereoselectivity of Addition of Organometallic Reagents to Pentodialdo-1,4-furanoses: Synthesis of L-Axenose and D-Evermicose from a Common Intermediate
  作者：Robert M. Giuliano、Frank J. Jr. Villani

  DOI：10.1021/jo00106a035

  日期：1995.1

  The additions of organometallic reagents to two pentodialdo-1,4-furanosides (methyl 3-O-benzyl-2-deoxy-alpha-D-erythro-pentofuranoside and its beta-anomer) were carried out under a variety of experimental conditions. Methylmagnesium halides, methyllithium, methylcerium and the organotitanium reagent MeTi(OiPr)(3) were reacted with the pentodialdo-1,4-furanosides in an effort to determine if the stereoselectivity of addition to the formyl group is the result of chelation or nonchelation control and to determine the effect of anomeric configuration. The stereochemistry of the products was assigned by NMR methods and correlation with known compounds synthesized previously. The stereoselectivity of addition depends on the configuration at the anomeric center of the dialdose, with the beta-anomer giving mainly the product of a non-chelation-controlled addition and the beta-anomer giving the opposite stereoselectivity. The major product obtained from the beta-anomer was utilized as a key intermediate in the synthesis of two branched-chain carbohydrates, axenose and evermicose, found in antibiotics. Methylcerium additions are the most efficient method for introducing the branching methyl group in a 2-deoxyfuranosid-3-ulose.