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Gold‐Catalyzed Intermolecular Addition of Carbonyl Compounds to 1,6‐Enynes: Reactivity, Scope, and Mechanistic Aspects
Author(s) -
Schelwies Mathias,
Moser Ralph,
Dempwolff Adrian L.,
Rominger Frank,
Helmchen Günter
Publication year - 2009
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200901614
Subject(s) - stereocenter , alkene , chemistry , cycloaddition , enyne , reactivity (psychology) , moiety , catalysis , intermolecular force , medicinal chemistry , combinatorial chemistry , stereochemistry , organic chemistry , molecule , enantioselective synthesis , medicine , alternative medicine , pathology
A full account of a recently discovered gold(I)‐catalyzed reaction, a cycloaddition of carbonyl compounds to enynes yielding 2‐oxabicyclo[3.1.0]hexanes with four stereogenic centers, is presented. The reaction proceeds with very high diastereoselectivity. The scope of the reaction has been investigated. In addition, experiments and DFT calculations concerning mechanistic aspects were carried out. The reaction course varies with the substitution pattern of the alkene moiety of the starting enyne. Branched olefins led to 2‐oxabicyclo[3.1.0]hexanes; terminally substituted olefins proceeded with the incorporation of two carbonyl components to give hexahydrocyclopenta[ d ][1,3]dioxines.