(-)-((1S,4R,5R)-4-(benzyloxy)-6,8-dioxabicyclo[3.2.1]oct-2-en-2-yl)((4aR,8R,8aR)-2,2-di-tert-butyl-8-((triisopropylsilyl)oxy)-4,4a,8,8a-tetrahydropyrano[3,2-d][1,3,2]dioxasilin-6-yl)methanone | 848864-30-2

• 分子结构分类: 有机化合物
• 英文名称: (-)-((1S,4R,5R)-4-(benzyloxy)-6,8-dioxabicyclo[3.2.1]oct-2-en-2-yl)((4aR,8R,8aR)-2,2-di-tert-butyl-8-((triisopropylsilyl)oxy)-4,4a,8,8a-tetrahydropyrano[3,2-d][1,3,2]dioxasilin-6-yl)methanone
• 英文别名: [(4aR,8R,8aR)-2,2-ditert-butyl-8-tri(propan-2-yl)silyloxy-4,4a,8,8a-tetrahydropyrano[3,2-d][1,3,2]dioxasilin-6-yl]-[(1S,4R,5R)-4-phenylmethoxy-6,8-dioxabicyclo[3.2.1]oct-2-en-2-yl]methanone
• CAS: 848864-30-2
• 化学式: C₃₇H₅₈O₈Si₂
• 分子量: 687.034
• InChiKey: FEJAPOCHEYYNDT-RUPDFSRRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.12
• 重原子数：
  47
• 可旋转键数：
  12
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  81.7
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  (-)-((1S,4R,5R)-4-(benzyloxy)-6,8-dioxabicyclo[3.2.1]oct-2-en-2-yl)((4aR,8R,8aR)-2,2-di-tert-butyl-8-((triisopropylsilyl)oxy)-4,4a,8,8a-tetrahydropyrano[3,2-d][1,3,2]dioxasilin-6-yl)methanone 在 hexacarbonyl molybdenum 硼烷四氢呋喃络合物 、 苯硅烷 、 potassium tri-sec-butyl-borohydride 、 对甲苯磺酸 作用下， 以 四氢呋喃 为溶剂， 反应 5.0h， 生成 (4aR,5S,8aS,9R,9aR,10aS)-5-((1S,2S,4R,5R)-4-Benzyloxy-6,8-dioxa-bicyclo[3.2.1]oct-2-yl)-2,2-di-tert-butyl-7,7-dimethyl-9-triisopropylsilanyloxy-hexahydro-1,3,6,8,10-pentaoxa-2-sila-anthracene
  参考文献：
  名称：

  C(1→4)-linked disaccharides through carbonylative Stille cross-coupling

  摘要：

  A tinglucal tributyl[4,6-O-bis(t-butyl)silylidene-3-O-tris(isopropyl)silyl]tin 7 and a triflate derived from isolevoglucosenone (1R,4R,5R)-4-benzyloxy-6,8-dioxabicyclo[3.2.1]oct-2-en-2-yl trifluoromethanesulfonate 10 undergo the carbonylative Stille condensation under special conditions requiring AsPh3, LiCl, and powdered charcoal as co-catalysts to give a cross-conjugated dienone 6 in which the bicyclic alkene moiety is more reactive than the glucal alkene moiety. This allows the regio- and stereoselective hydrogenation of the bicyclic alkene moiety giving an enone 21 that can be reduced stereoselectively to an allylic alcohol 22. Hydroboration of the glucal and bicyclic acetal opening generates a C(1-->4) linked disaccharide 25 in which a protected form of beta-D-glucopyranose is attached at position C(4) of a alpha-D-3-deoxy-ribo-hexopyranoside derivative via a (S)-hydroxymethano linker. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2004.11.048
• 作为产物：
  描述：

  一氧化碳 、 (4aR,8R,8aR)-2,2-Di-tert-butyl-6-tributylstannanyl-8-triisopropylsilanyloxy-4,4a,8,8a-tetrahydro-1,3,5-trioxa-2-sila-naphthalene 、 (1R,4R,5R)-4-benzyloxy-6,8-dioxabicyclo[3.2.1]oct-2-en-2-yl trifluoromethanesulfonate 在 tris(dibenzylideneacetone)dipalladium (0) 三苯胂 、 甲烷 、 lithium chloride 作用下， 以 N-甲基吡咯烷酮 为溶剂， 50.0 ℃ 、5.0 MPa 条件下， 反应 18.0h， 以79%的产率得到(-)-((1S,4R,5R)-4-(benzyloxy)-6,8-dioxabicyclo[3.2.1]oct-2-en-2-yl)((4aR,8R,8aR)-2,2-di-tert-butyl-8-((triisopropylsilyl)oxy)-4,4a,8,8a-tetrahydropyrano[3,2-d][1,3,2]dioxasilin-6-yl)methanone
  参考文献：
  名称：

  C(1→4)-linked disaccharides through carbonylative Stille cross-coupling

  摘要：

  A tinglucal tributyl[4,6-O-bis(t-butyl)silylidene-3-O-tris(isopropyl)silyl]tin 7 and a triflate derived from isolevoglucosenone (1R,4R,5R)-4-benzyloxy-6,8-dioxabicyclo[3.2.1]oct-2-en-2-yl trifluoromethanesulfonate 10 undergo the carbonylative Stille condensation under special conditions requiring AsPh3, LiCl, and powdered charcoal as co-catalysts to give a cross-conjugated dienone 6 in which the bicyclic alkene moiety is more reactive than the glucal alkene moiety. This allows the regio- and stereoselective hydrogenation of the bicyclic alkene moiety giving an enone 21 that can be reduced stereoselectively to an allylic alcohol 22. Hydroboration of the glucal and bicyclic acetal opening generates a C(1-->4) linked disaccharide 25 in which a protected form of beta-D-glucopyranose is attached at position C(4) of a alpha-D-3-deoxy-ribo-hexopyranoside derivative via a (S)-hydroxymethano linker. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2004.11.048