Annulated N-Heterocycles by Tandem Gold(I)-Catalyzed [3,3]-Rearrangement/Nazarov Reaction of Propargylic Ester Derivatives: an Experimental and Computational Study

Autor:	Dina Scarpi, Béla Fiser, Enrique Gómez-Bengoa, Martina Petrović, Ernesto G. Occhiato
Rok vydání:	2015
Předmět:	Annulation Organic Chemistry Regioselectivity Sonogashira coupling Enol Combinatorial chemistry Catalysis Reaction rate chemistry.chemical_compound chemistry Torquoselectivity Propargyl Organic chemistry Physical and Theoretical Chemistry
Zdroj:	European Journal of Organic Chemistry. 2015:3943-3956
ISSN:	1434-193X
DOI:	10.1002/ejoc.201500462
Popis:	The gold(I)-catalyzed tandem rearrangement/Nazarov reaction of propargylic ester derivatives is a useful strategy for the synthesis of cyclopenta-fused N-heterocyclic structures present in many natural compounds. Readily available lactams are converted into enol phosphates and triflates and coupled to propargyl alcohols under Sonogashira conditions. After acetylation, the gold-catalyzed rearrangement of the enynyl acetates readily occurs when using 3–5 mol-% of a gold(I) catalyst. The rearrangement generates a divinyl cation which undergoes a 4π electrocyclization (Nazarov reaction) leading to the target compound in good to excellent yield. This process has been studied in details both experimentally and computationally to understand the influence of both the reaction conditions and substrate structural features on the reaction rate and regioselectivity, as well as the torquoselectivity in the ring closure step. A series of examples illustrates at the end the scope of the reaction.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::94fe8b7b60efd00960bee2a33e0aa923 https://doi.org/10.1002/ejoc.201500462 Zobrazit plný text záznamu Plný text ve formátu PDF Plný text ve formátu HTML
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