methyl 2-[(tert-butoxycarbonyl)amino]-6{[tert-butyl(diphenyl)silyl]oxy}-4-hexynoate | 889670-04-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: methyl 2-[(tert-butoxycarbonyl)amino]-6{[tert-butyl(diphenyl)silyl]oxy}-4-hexynoate
• 英文别名: Methyl 6-[tert-butyl(diphenyl)silyl]oxy-2-[(2-methylpropan-2-yl)oxycarbonylamino]hex-4-ynoate
• CAS: 889670-04-6
• 化学式: C₂₈H₃₇NO₅Si
• 分子量: 495.691
• InChiKey: VMBSVHLFSVBNHE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.02
• 重原子数：
  35
• 可旋转键数：
  11
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  73.9
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  methyl 2-[(tert-butoxycarbonyl)amino]-6{[tert-butyl(diphenyl)silyl]oxy}-4-hexynoate 在 palladium on barium sulfate 氢气 、 sodium tetrahydroborate 作用下， 以 乙酸乙酯 、 Petroleum ether 、 甲醇 为溶剂， 反应 32.0h， 生成 tert-butyl (Z)-5-{[tert-butyl(diphenyl)silyl]oxy}-1-(hydroxymethyl)-3,4-dimethyl-3-pentenyl-carbamate 、 tert-butyl N-[6-[tert-butyl(diphenyl)silyl]oxy-1-hydroxyhexan-2-yl]carbamate
  参考文献：
  名称：

  A Diastereoselective Radical Cyclization Approach to Substituted Quinuclidines

  摘要：

  A new, concise, and flexible approach to novel quinuclidines has been developed, which employs a phosphorus hydride mediated radical addition/cyclization reaction in the key step. 1,7-Diene 5 reacts with diethyl thiophosphite in an efficient and diastereoselective radical addition/cyclization reaction to give trisubstituted piperidines 4ab. Piperidines 4ab are subsequently converted into 2,5-disubstituted quinuclidines using S(N)2-type cyclizations. Finally, the resulting quinuclidines are shown to undergo novel Horner-Wadsworth Emmons-type (HWE-type) reactions to give unsaturated quinuclidines 21a and 21b, which have structures similar to that of (-)-quinine 1.

  DOI：

  10.1021/jo060349q
• 作为产物：
  描述：

  tert-butyl(diphenyl)(2-propynyloxy)silane 在 正丁基锂 、 三甲基氯硅烷 、 1,2-二溴乙烷 、 锌 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 22.95h， 生成 methyl 2-[(tert-butoxycarbonyl)amino]-6{[tert-butyl(diphenyl)silyl]oxy}-4-hexynoate
  参考文献：
  名称：

  A Diastereoselective Radical Cyclization Approach to Substituted Quinuclidines

  摘要：

  A new, concise, and flexible approach to novel quinuclidines has been developed, which employs a phosphorus hydride mediated radical addition/cyclization reaction in the key step. 1,7-Diene 5 reacts with diethyl thiophosphite in an efficient and diastereoselective radical addition/cyclization reaction to give trisubstituted piperidines 4ab. Piperidines 4ab are subsequently converted into 2,5-disubstituted quinuclidines using S(N)2-type cyclizations. Finally, the resulting quinuclidines are shown to undergo novel Horner-Wadsworth Emmons-type (HWE-type) reactions to give unsaturated quinuclidines 21a and 21b, which have structures similar to that of (-)-quinine 1.

  DOI：

  10.1021/jo060349q

文献信息

• A Diastereoselective Radical Cyclization Approach to Substituted Quinuclidines
  作者：Thomas A. Hunt、Andrew F. Parsons、Robert Pratt

  DOI：10.1021/jo060349q

  日期：2006.4.1

  A new, concise, and flexible approach to novel quinuclidines has been developed, which employs a phosphorus hydride mediated radical addition/cyclization reaction in the key step. 1,7-Diene 5 reacts with diethyl thiophosphite in an efficient and diastereoselective radical addition/cyclization reaction to give trisubstituted piperidines 4ab. Piperidines 4ab are subsequently converted into 2,5-disubstituted quinuclidines using S(N)2-type cyclizations. Finally, the resulting quinuclidines are shown to undergo novel Horner-Wadsworth Emmons-type (HWE-type) reactions to give unsaturated quinuclidines 21a and 21b, which have structures similar to that of (-)-quinine 1.