tert-butyl [(2S,3R)-3-{[(2,3-dimethylbutan-2-yl)dimethylsilyl]oxy}-1-oxo-1-({(S)-quinolin-4-yl-[(1S,2S,4S,5R)-5-vinylquinuclidin-2-yl]methyl}amino)butan-2-yl]carbamate | 1381859-81-9

• 分子结构分类: 有机化合物 - 生物碱及其衍生物 - 金鸡纳生物碱
• 英文名称: tert-butyl [(2S,3R)-3-{[(2,3-dimethylbutan-2-yl)dimethylsilyl]oxy}-1-oxo-1-({(S)-quinolin-4-yl-[(1S,2S,4S,5R)-5-vinylquinuclidin-2-yl]methyl}amino)butan-2-yl]carbamate
• 英文别名: tert-butyl ((2S,3R)-3-(((2,3-dimethylbutan-2-yl)dimethylsilyl)oxy)-1-oxo-1-(((S)-quinolin-4-yl((1S,2S,4S,5R)-5-vinylquinuclidin-2-yl)methyl)amino)butan-2-yl)carbamate
• CAS: 1381859-81-9
• 化学式: C₃₆H₅₆N₄O₄Si
• 分子量: 636.951
• InChiKey: CADVPIAZBQHCFI-CFRHILBGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.23
• 重原子数：
  45.0
• 可旋转键数：
  11.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  92.79
• 氢给体数：
  2.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  tert-butyl [(2S,3R)-3-{[(2,3-dimethylbutan-2-yl)dimethylsilyl]oxy}-1-oxo-1-({(S)-quinolin-4-yl-[(1S,2S,4S,5R)-5-vinylquinuclidin-2-yl]methyl}amino)butan-2-yl]carbamate 在 三氟乙酸 、 碳酸氢钠 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 12.0h， 生成 (2S,3R)-2-amino-3-(((2,3-dimethylbutan-2-yl)dimethylsilyl)oxy)-N-((S)-quinolin-4-yl((1S,2S,4S,5R)-5-vinylquinuclidin-2-yl)methyl)butanamide
  参考文献：
  名称：

  Highly Enantioselective Regiodivergent Allylic Alkylations of MBH Carbonates with Phthalides

  摘要：

  Phthalides were used for the first time in the allylic alkylation reactions with MBH carbonates for the creation of chiral 3,3-disubstituted phthalides. Highly enantioselective regiodivergent synthesis of gamma-selective or beta-selective allylic alkylation products was achieved by employing bifunctional chiral phosphines or multifunctional tertiary amine-thioureas as the catalyst, respectively. It was demonstrated that proper selection of catalysts and reaction conditions would differentiate an S(N)2'-S(N)2' pathway and an addition-elimination process, yielding different regioisomers of the allylic alkylation products in a highly enantiomerically pure form.

  DOI：

  10.1021/ja303115m
• 作为产物：
  描述：

  二碳酸二叔丁酯 在 咪唑 、 碳酸氢钠 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 15.0h， 生成 tert-butyl [(2S,3R)-3-{[(2,3-dimethylbutan-2-yl)dimethylsilyl]oxy}-1-oxo-1-({(S)-quinolin-4-yl-[(1S,2S,4S,5R)-5-vinylquinuclidin-2-yl]methyl}amino)butan-2-yl]carbamate
  参考文献：
  名称：

  Highly Enantioselective Regiodivergent Allylic Alkylations of MBH Carbonates with Phthalides

  摘要：

  Phthalides were used for the first time in the allylic alkylation reactions with MBH carbonates for the creation of chiral 3,3-disubstituted phthalides. Highly enantioselective regiodivergent synthesis of gamma-selective or beta-selective allylic alkylation products was achieved by employing bifunctional chiral phosphines or multifunctional tertiary amine-thioureas as the catalyst, respectively. It was demonstrated that proper selection of catalysts and reaction conditions would differentiate an S(N)2'-S(N)2' pathway and an addition-elimination process, yielding different regioisomers of the allylic alkylation products in a highly enantiomerically pure form.

  DOI：

  10.1021/ja303115m

文献信息

• Diastereodivergent Synthesis of 3‐Spirocyclopropyl‐2‐oxindoles through Direct Enantioselective Cyclopropanation of Oxindoles
  作者：Xiaowei Dou、Yixin Lu

  DOI：10.1002/chem.201200655

  日期：2012.7.2

  reaction of oxindole was developed, in which oxindoles were employed as a dinucleophilic C1 synthon and bromonitroolefins with a dielectrophilic center were used as a C2 synthon (see scheme). An amino acid based multifunctional catalyst promoted the [2+1] reaction, giving the products in high yields and excellent enantioselectivities. A divergent synthesis of different stereoisomers of 3‐spirocyclopropyl‐2‐oxindoles

  像多米诺骨牌一样倒下：首次发现了羟吲哚的直接有机催化不对称环丙烷化反应，其中将羟吲哚用作双亲核C 1合成子，将具有双亲电子中心的溴硝基烯烃用作C 2合成子（参见方案）。基于氨基酸的多功能催化剂促进了[2 + 1]反应，从而以高收率和优异的对映选择性提供了产物。实现了3-螺环丙基-2-氧吲哚不同立体异构体的多样化合成。