Bromo-acetic acid (1R,2S,4S,5R)-2-(tert-butyl-diphenyl-silanyloxy)-3-[(Z)-methoxyimino]-6,8-dioxa-bicyclo[3.2.1]oct-4-yl ester | 190188-89-7

• 英文名称: Bromo-acetic acid (1R,2S,4S,5R)-2-(tert-butyl-diphenyl-silanyloxy)-3-[(Z)-methoxyimino]-6,8-dioxa-bicyclo[3.2.1]oct-4-yl ester
• CAS: 190188-89-7
• 化学式: C₂₅H₃₀BrNO₆Si
• 分子量: 548.506
• InChiKey: DHSDVBCEPLDCDT-OUJCMCIWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.0
• 重原子数：
  34.0
• 可旋转键数：
  7.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  75.58
• 氢给体数：
  0.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  Bromo-acetic acid (1R,2S,4S,5R)-2-(tert-butyl-diphenyl-silanyloxy)-3-[(Z)-methoxyimino]-6,8-dioxa-bicyclo[3.2.1]oct-4-yl ester 在 偶氮二异丁腈 、 三正丁基氢锡 、 sodium hydride 作用下， 以 甲苯 为溶剂， 生成 (Z)-1,6-anhydro-4-O-(tert-butyldiphenylsilyl)-3-deoxy-3-methoxyimine-2-O-(prop-2'-inyl)-β-D-arabino-hexopyranose
  参考文献：
  名称：

  Radical cyclisation onto C-3 of 1,6-anhydro-β-d-mannopyranose derivatives. Application to the formation of the C8a centre of (−)-tetrodotoxin

  摘要：

  Starting from 1,6-anhydro-beta-D-mannopyranose, compounds 7a-d, which have a ketoxime ether at C3 and a carbon radical precursor tethered to the hydroxyl group at position 2, were efficiently prepared. While alkyl pi-radicals derived from 7a and 7b failed to cyclize, the vinyl sigma-radicals derived from 7c and 7d underwent the desired 1,5-exo cyclization, affording advanced precursors of (-)-tetrodotoxin. This type of transformation should be useful for the formation of sterically crowded nitrogen-bearing carbon centers in carbohydrate-derived substrates. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4039(97)00460-7
• 作为产物：
  描述：

  (3Z)-1,6-anhydro-4-O-(tert-butyldiphenylsilyl)-2-O-(1'-ethoxy-2'-iodoethyl)-3-deoxy-3-methoxyimine-β-D-arabino-hexopyranose 在 偶氮二异丁腈 、 三丁基氯化锡 、 sodium cyanoborohydride 、 三乙胺 作用下， 以 二氯甲烷 、 叔丁醇 为溶剂， 反应 6.0h， 生成 Bromo-acetic acid (1R,2S,4S,5R)-2-(tert-butyl-diphenyl-silanyloxy)-3-[(Z)-methoxyimino]-6,8-dioxa-bicyclo[3.2.1]oct-4-yl ester
  参考文献：
  名称：

  Radical cyclisation onto C-3 of 1,6-anhydro-β-d-mannopyranose derivatives. Application to the formation of the C8a centre of (−)-tetrodotoxin

  摘要：

  Starting from 1,6-anhydro-beta-D-mannopyranose, compounds 7a-d, which have a ketoxime ether at C3 and a carbon radical precursor tethered to the hydroxyl group at position 2, were efficiently prepared. While alkyl pi-radicals derived from 7a and 7b failed to cyclize, the vinyl sigma-radicals derived from 7c and 7d underwent the desired 1,5-exo cyclization, affording advanced precursors of (-)-tetrodotoxin. This type of transformation should be useful for the formation of sterically crowded nitrogen-bearing carbon centers in carbohydrate-derived substrates. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4039(97)00460-7