(2-methyl-5-tert-butylphenyl) 3-O-acetyl-2,7-di-O-benzyl-4-O,6-S-(1-cyano)benzylidene-D-glycero-1,6-dithio-α-D-mannoheptopyranoside | 1442422-67-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (2-methyl-5-tert-butylphenyl) 3-O-acetyl-2,7-di-O-benzyl-4-O,6-S-(1-cyano)benzylidene-D-glycero-1,6-dithio-α-D-mannoheptopyranoside
• 英文别名: [(2R,4R,4aS,6R,7S,8S,8aS)-6-(5-tert-butyl-2-methylphenyl)sulfanyl-2-cyano-2-phenyl-7-phenylmethoxy-4-(phenylmethoxymethyl)-4,4a,6,7,8,8a-hexahydropyrano[2,3-e][1,3]oxathiin-8-yl] acetate
• CAS: 1442422-67-4
• 化学式: C₄₂H₄₅NO₆S₂
• 分子量: 723.954
• InChiKey: OYSUOTRAUDFHBX-VLMSDLFGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.9
• 重原子数：
  51
• 可旋转键数：
  13
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  138
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  (2-methyl-5-tert-butylphenyl) 3-O-acetyl-2,7-di-O-benzyl-4-O,6-S-(1-cyano)benzylidene-D-glycero-1,6-dithio-α-D-mannoheptopyranoside 、 6-羟基己酸叔丁酯 在 三氟甲磺酸酐 、 二苯基亚砜 、 2,4,6-三叔丁基嘧啶 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 以96%的产率得到5-tert-butyloxycarbonylpentyl 3-O-acetyl-2,7-di-O-benzyl-4-O,6-S-(1-cyano)benzylidene-D-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) 2-O-benzyl-4-O-(p-methoxybenzyl)-3-O-(2-naphthalenylmethyl)-L-glycero-1-thia-α-D-mannoheptopyranoside 在 4-二甲氨基吡啶 、 lithium aluminium tetrahydride 、 camphor-10-sulfonic acid 、 三氟化硼乙醚 、 水 、 sodium hexamethyldisilazane 、 二正丁基氧化锡 、 2-[N,正双(三氟甲烷烷磺酰)氨基]-5-氯吡啶 、 N,N-二异丙基乙胺 、 三氟乙酸 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 、 甲苯 为溶剂， 反应 32.7h， 生成 (2-methyl-5-tert-butylphenyl) 3-O-acetyl-2,7-di-O-benzyl-4-O,6-S-(1-cyano)benzylidene-D-glycero-1,6-dithio-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