methyl [(2-methyl-5-tertbutylphenyl)2-O-benzyl-4-O-(p-methoxybenzyl)-3-O-(2-naphthalenylmethyl)-L-glycero-1-thia-a-D-mannoheptopyranosyl urinate] | 1442422-61-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl [(2-methyl-5-tertbutylphenyl)2-O-benzyl-4-O-(p-methoxybenzyl)-3-O-(2-naphthalenylmethyl)-L-glycero-1-thia-a-D-mannoheptopyranosyl urinate]
• CAS: 1442422-61-8
• 化学式: C₄₅H₅₀O₈S
• 分子量: 750.953
• InChiKey: YPJIXAMXHYTXNR-KHZROVHDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.56
• 重原子数：
  54.0
• 可旋转键数：
  14.0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  92.68
• 氢给体数：
  1.0
• 氢受体数：
  9.0

反应信息

• 作为反应物：
  描述：

  methyl [(2-methyl-5-tertbutylphenyl)2-O-benzyl-4-O-(p-methoxybenzyl)-3-O-(2-naphthalenylmethyl)-L-glycero-1-thia-a-D-mannoheptopyranosyl urinate] 在 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 为溶剂， 反应 4.17h， 以90%的产率得到(2-methyl-5-tert-butylphenyl) 2-O-benzyl-4-O-(p-methoxybenzyl)-3-O-(2-naphthalenylmethyl)-L-glycero-1-thia-α-D-mannoheptopyranoside
  参考文献：
  名称：

  Improved methods for the stereoselective synthesis of mannoheptosyl donors and their glycosides: toward the synthesis of the trisaccharide repeating unit of the Campylobacter jejuni RM1221 capsular polysaccharide

  摘要：

  In view of the importance of 6-deoxymannoheptosides as structural units in the Campylobacter jejuni RM1221 capsular polysaccharide, the development of effective synthetic protocols for 4-O-6-S-alpha-cyanobenzylidene thio-o-mannoheptapyranoside donors carrying either 3-O-naphthylmethyl or 3-O-acetyl groups is described starting from D-mannose. In particular, tris(phenylthio)methyllithium is found to undergo highly stereoselective addition to a mannose-6-aldehyde in sharp contrast to the vinyl Grignard reagent whose reactions were essentially devoid of selectivity. A brief survey of coupling reactions with the two donors indicted the 3-O-acetyl system to be highly alpha-selective whereas the 3-O-naphthylmethyl congener was highly beta-selective indicating that the presence of the seventh carbon atom in these donors is not detrimental to coupling selectivity in either instance. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2013.04.094
• 作为产物：
  描述：

  (2-methyl-5-tert-butylphenyl) 1-thio-α-D-mannopyranoside 在 正丁基锂 、 草酰氯 、 sodium hydride 、 二异丁基氢化铝 、 二正丁基氧化锡 、 对甲苯磺酸 、 二甲基亚砜 、 copper(II) oxide 、 copper dichloride 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 32.67h， 生成 S-phenyl [(2-methyl-5-tert-butylphenyl) 2-O-benzyl-4-O-(p-methoxybenzyl)-3-O-(2-naphthalenylmethyl)-L-glycero-1-thia-α-D-mannoheptopyranosylurinate] 、 methyl [(2-methyl-5-tertbutylphenyl)2-O-benzyl-4-O-(p-methoxybenzyl)-3-O-(2-naphthalenylmethyl)-L-glycero-1-thia-a-D-mannoheptopyranosyl urinate]
  参考文献：
  名称：

  Improved methods for the stereoselective synthesis of mannoheptosyl donors and their glycosides: toward the synthesis of the trisaccharide repeating unit of the Campylobacter jejuni RM1221 capsular polysaccharide

  摘要：

  In view of the importance of 6-deoxymannoheptosides as structural units in the Campylobacter jejuni RM1221 capsular polysaccharide, the development of effective synthetic protocols for 4-O-6-S-alpha-cyanobenzylidene thio-o-mannoheptapyranoside donors carrying either 3-O-naphthylmethyl or 3-O-acetyl groups is described starting from D-mannose. In particular, tris(phenylthio)methyllithium is found to undergo highly stereoselective addition to a mannose-6-aldehyde in sharp contrast to the vinyl Grignard reagent whose reactions were essentially devoid of selectivity. A brief survey of coupling reactions with the two donors indicted the 3-O-acetyl system to be highly alpha-selective whereas the 3-O-naphthylmethyl congener was highly beta-selective indicating that the presence of the seventh carbon atom in these donors is not detrimental to coupling selectivity in either instance. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2013.04.094