phenyl 2-O-benzyl-6,7-dideoxy-4-O-(p-methoxybenzyl)-3-O-(2-naphthalenylmethyl)-α-D-thiohept-6-enopyranoside | 902751-25-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: phenyl 2-O-benzyl-6,7-dideoxy-4-O-(p-methoxybenzyl)-3-O-(2-naphthalenylmethyl)-α-D-thiohept-6-enopyranoside
• 英文别名: (2R,3R,4S,5S,6R)-2-ethenyl-3-[(4-methoxyphenyl)methoxy]-4-(naphthalen-2-ylmethoxy)-5-phenylmethoxy-6-phenylsulfanyloxane
• CAS: 902751-25-1
• 化学式: C₃₉H₃₈O₅S
• 分子量: 618.794
• InChiKey: KYQDYIMGYSSLTF-WEMFOFRKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.4
• 重原子数：
  45
• 可旋转键数：
  13
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  71.4
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  phenyl 2-O-benzyl-6,7-dideoxy-4-O-(p-methoxybenzyl)-3-O-(2-naphthalenylmethyl)-α-D-thiohept-6-enopyranoside 在 四氧化锇 、 2-氯-N-(2-氯乙基)-N-甲基乙胺氧化物 、 三氟甲磺酸酐 、 二苯基亚砜 、 偶氮二甲酸二异丙酯 、 camphor-10-sulfonic acid 、 potassium carbonate 、 三苯基膦 、 三氟乙酸 、 2,4,6-三叔丁基嘧啶 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 水 、 丙酮 、 叔丁醇 为溶剂， 反应 38.5h， 生成 methyl 2,7-di-O-benzyl-4,6-O-{1-cyano-2-(2-iodophenyl)ethylidene}-3-O-(2-naphthalenylmethyl)-D-glycero-β-D-manno-heptopyranosyl-(1->4)-2,3-O-isopropylidene-α-L-rhamnopyranoside
  参考文献：
  名称：

  Stereocontrolled Synthesis of the d- and l-glycero-β-d-manno-Heptopyranosides and Their 6-Deoxy Analogues. Synthesis of Methyl α-l-Rhamno-pyranosyl-(1→3)-d-glycero-β-d-manno-heptopyranosyl- (1→3)-6-deoxy-glycero-β-d-manno-heptopyranosyl-(1→4)-α-l- rhamno-pyranoside, a Tetrasaccharide Subunit of the Lipopolysaccharide from Plesimonas shigelloides

  摘要：

  The synthesis of D-and L-glycero-alpha-manno-thioheptopyranosides, protected with 4,6-O-alkylidenetype acetals is described. In glycosylations carried out with preactivation with the 1-benzenesulfinylpiperidine/trifluoromethanesulfonic anhydride couple, both the D-and L-glycero series exhibit excellent, beta-selectivity with a range of glycosyl acceptors. In contrast, a 4,7-O-alkylidene acetal was found not to afford, beta-selectivity. With a 4,6-O-[1-cyano-2-(2-iodophenyl) ethylidene] acetal protected thioglycoside, excellent, beta-selectivity was obtained in glycosylation reactions, and subsequent treatment with tributyltin hydride and azoisobutyronitrile brought about clean fragmentation to the 6-deoxy-glycero-beta-D-manno-heptopyranosides. This chemistry was applied to the stereocontrolled synthesis of methyl alpha-L-rhamno-pyranosyl-(1 -> 3)-D-glycero-beta- D-manno-heptopyranosyl-(1 -> 3)-6-deoxy-glycero-beta-D-manno-heptopyranosyl-(1 -> 4)-alpha-L-rhamno-pyranoside, a component of the lipopolysaccharide from Plesimonas shigelloides.

  DOI：

  10.1021/ja061594u
• 作为产物：
  描述：

  2-溴甲基萘 在 草酰氯 、 二异丁基氢化铝 、 二正丁基氧化锡 、 二甲基亚砜 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 27.0h， 生成 phenyl 2-O-benzyl-6,7-dideoxy-4-O-(p-methoxybenzyl)-3-O-(2-naphthalenylmethyl)-α-D-thiohept-6-enopyranoside
  参考文献：
  名称：

  Stereocontrolled Synthesis of the d- and l-glycero-β-d-manno-Heptopyranosides and Their 6-Deoxy Analogues. Synthesis of Methyl α-l-Rhamno-pyranosyl-(1→3)-d-glycero-β-d-manno-heptopyranosyl- (1→3)-6-deoxy-glycero-β-d-manno-heptopyranosyl-(1→4)-α-l- rhamno-pyranoside, a Tetrasaccharide Subunit of the Lipopolysaccharide from Plesimonas shigelloides

  摘要：

  The synthesis of D-and L-glycero-alpha-manno-thioheptopyranosides, protected with 4,6-O-alkylidenetype acetals is described. In glycosylations carried out with preactivation with the 1-benzenesulfinylpiperidine/trifluoromethanesulfonic anhydride couple, both the D-and L-glycero series exhibit excellent, beta-selectivity with a range of glycosyl acceptors. In contrast, a 4,7-O-alkylidene acetal was found not to afford, beta-selectivity. With a 4,6-O-[1-cyano-2-(2-iodophenyl) ethylidene] acetal protected thioglycoside, excellent, beta-selectivity was obtained in glycosylation reactions, and subsequent treatment with tributyltin hydride and azoisobutyronitrile brought about clean fragmentation to the 6-deoxy-glycero-beta-D-manno-heptopyranosides. This chemistry was applied to the stereocontrolled synthesis of methyl alpha-L-rhamno-pyranosyl-(1 -> 3)-D-glycero-beta- D-manno-heptopyranosyl-(1 -> 3)-6-deoxy-glycero-beta-D-manno-heptopyranosyl-(1 -> 4)-alpha-L-rhamno-pyranoside, a component of the lipopolysaccharide from Plesimonas shigelloides.

  DOI：

  10.1021/ja061594u

文献信息

• Stereocontrolled Synthesis of the <scp>d</scp>- and <scp>l</scp>-<i>glycero</i>-β-<scp>d</scp>-<i>manno</i>-Heptopyranosides and Their 6-Deoxy Analogues. Synthesis of Methyl α-<scp>l</scp>-<i>Rhamno</i>-pyranosyl-(1→3)-<scp>d</scp>-<i>glycero</i>-β-<scp>d</scp>-<i>manno</i>-heptopyranosyl- (1→3)-6-deoxy-<i>glycero</i>-β-<scp>d</scp>-<i>manno</i>-heptopyranosyl-(1→4)-α-<scp>l</scp>- <i>rhamno</i>-pyranoside, a Tetrasaccharide Subunit of the Lipopolysaccharide from <i>Plesimonas shigelloides</i>
  作者：David Crich、Abhisek Banerjee

  DOI：10.1021/ja061594u

  日期：2006.6.1

  The synthesis of D-and L-glycero-alpha-manno-thioheptopyranosides, protected with 4,6-O-alkylidenetype acetals is described. In glycosylations carried out with preactivation with the 1-benzenesulfinylpiperidine/trifluoromethanesulfonic anhydride couple, both the D-and L-glycero series exhibit excellent, beta-selectivity with a range of glycosyl acceptors. In contrast, a 4,7-O-alkylidene acetal was found not to afford, beta-selectivity. With a 4,6-O-[1-cyano-2-(2-iodophenyl) ethylidene] acetal protected thioglycoside, excellent, beta-selectivity was obtained in glycosylation reactions, and subsequent treatment with tributyltin hydride and azoisobutyronitrile brought about clean fragmentation to the 6-deoxy-glycero-beta-D-manno-heptopyranosides. This chemistry was applied to the stereocontrolled synthesis of methyl alpha-L-rhamno-pyranosyl-(1 -> 3)-D-glycero-beta- D-manno-heptopyranosyl-(1 -> 3)-6-deoxy-glycero-beta-D-manno-heptopyranosyl-(1 -> 4)-alpha-L-rhamno-pyranoside, a component of the lipopolysaccharide from Plesimonas shigelloides.