Medium-Ring Effects on the Endo/Exo Selectivity of the Organocatalytic Intramolecular Diels鈥揂lder Reaction
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- 作者：Joel F. Hooper ; Natalie C. James ; Esra Bozkurt ; Viktorya Aviyente ; Jonathan M. White ; Mareike C. Holland ; Ryan Gilmour ; Andrew B. Holmes ; K. N. Houk
- 刊名：Journal of Organic Chemistry
- 出版年：2015
- 出版时间：December 18, 2015
- 年：2015
- 卷：80
- 期：24
- 页码：12058-12075
- 全文大小：1092K
- ISSN：1520-6904
文摘
The intramolecular Diels鈥揂lder reaction has been used as a powerful method to access the tricyclic core of the eunicellin natural products from a number of 9-membered-ring precursors. The endo/exo selectivity of this reaction can be controlled through a remarkable organocatalytic approach, employing MacMillan鈥檚 imidazolidinone catalysts, although the mechanistic origin of this selectivity remains unclear. We present a combined experimental and density functional theory investigation, providing insight into the effects of medium-ring constraints on the organocatalyzed intramolecular Diels鈥揂lder reaction to form the isobenzofuran core of the eunicellins.