Hooper Joel F, James Natalie C, Bozkurt Esra, Aviyente Viktorya, White Jonathan M, Holland Mareike C, Gilmour Ryan, Holmes Andrew B, Houk K N
School of Chemistry, Bio21 Institute, The University of Melbourne , 30 Flemington Road, Melbourne, Victoria 3010, Australia.
Department of Chemistry and Biochemistry, University of California , Los Angeles, California 90095, United States.
J Org Chem. 2015 Dec 18;80(24):12058-75. doi: 10.1021/acs.joc.5b02037. Epub 2015 Nov 30.
The intramolecular Diels-Alder 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's 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-Alder reaction to form the isobenzofuran core of the eunicellins.
分子内狄尔斯-阿尔德反应已被用作一种强大的方法，从多种九元环前体合成海兔毒素天然产物的三环核心。尽管该反应的内型/外型选择性的机理起源尚不清楚，但通过采用麦克米伦咪唑烷酮催化剂的显著有机催化方法，可以控制该反应的内型/外型选择性。我们进行了一项结合实验和密度泛函理论的研究，以深入了解中环限制对形成海兔毒素异苯并呋喃核心的有机催化分子内狄尔斯-阿尔德反应的影响。
