4.7 Article

Formation of Aza-ortho-quinone Methides Under Room Temperature Conditions: Cs2CO3 Effect

期刊

JOURNAL OF ORGANIC CHEMISTRY
卷 82, 期 14, 页码 7183-7189

出版社

AMER CHEMICAL SOC
DOI: 10.1021/acs.joc.7b00697

关键词

-

资金

  1. Stone family
  2. National Science Foundation (NSF) [CHE-1352663]
  3. National Institutes of Health [NIGMS R01 GM073072]
  4. Johnson Research Fellowship

向作者/读者索取更多资源

Since the first report of a facile, room temperature process to access aza-ortho-quinone methides (aoQMs) by Corey in 1999, this chemistry has remained dormant until our report of an enantioselective catalytic example in 2014. We report a theoretical and experimental study of the key to success behind these successful examples to enable broader exploitation of this useful intermediate. We have discovered that transformations involving the aoQM are remarkably facile with barriers <17 kcal/mol. The main difficulty of exploiting aoQM in synthesis is that they are unstable (Delta G > 30 kcal/mol), precluding their formation under mild conditions. The use of Cs2CO3 as base is critical. It provides a thermodynamically and kinetically favorable means to form aoQMs, independent of the salt solubility and base strength. The exothermic formation of salt byproducts provides a driving force (average Delta G = 30.8 kcal/mol) compensating for the majority of the inherent unfavorable thermodynamics of aoQM formation.

作者

我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。

评论

主要评分

4.7
评分不足

次要评分

新颖性
-
重要性
-
科学严谨性
-
评价这篇论文

推荐

暂无数据
暂无数据