Brook Rearrangement as a Trigger for the Ring Opening of Strained Carbocycles
Dr. Fa-Guang Zhang
The Mallat Family Laboratory of Organic Chemistry, Schulich Faculty of Chemistry and Lise Meitner-Minerva Center for Computational Quantum Chemistry, Technion-Israel Institute of Technology, Haifa, 32000 (Israel)
Search for more papers by this authorDr. Guillaume Eppe
The Mallat Family Laboratory of Organic Chemistry, Schulich Faculty of Chemistry and Lise Meitner-Minerva Center for Computational Quantum Chemistry, Technion-Israel Institute of Technology, Haifa, 32000 (Israel)
Search for more papers by this authorCorresponding Author
Prof. Dr. Ilan Marek
The Mallat Family Laboratory of Organic Chemistry, Schulich Faculty of Chemistry and Lise Meitner-Minerva Center for Computational Quantum Chemistry, Technion-Israel Institute of Technology, Haifa, 32000 (Israel)
The Mallat Family Laboratory of Organic Chemistry, Schulich Faculty of Chemistry and Lise Meitner-Minerva Center for Computational Quantum Chemistry, Technion-Israel Institute of Technology, Haifa, 32000 (Israel)Search for more papers by this authorDr. Fa-Guang Zhang
The Mallat Family Laboratory of Organic Chemistry, Schulich Faculty of Chemistry and Lise Meitner-Minerva Center for Computational Quantum Chemistry, Technion-Israel Institute of Technology, Haifa, 32000 (Israel)
Search for more papers by this authorDr. Guillaume Eppe
The Mallat Family Laboratory of Organic Chemistry, Schulich Faculty of Chemistry and Lise Meitner-Minerva Center for Computational Quantum Chemistry, Technion-Israel Institute of Technology, Haifa, 32000 (Israel)
Search for more papers by this authorCorresponding Author
Prof. Dr. Ilan Marek
The Mallat Family Laboratory of Organic Chemistry, Schulich Faculty of Chemistry and Lise Meitner-Minerva Center for Computational Quantum Chemistry, Technion-Israel Institute of Technology, Haifa, 32000 (Israel)
The Mallat Family Laboratory of Organic Chemistry, Schulich Faculty of Chemistry and Lise Meitner-Minerva Center for Computational Quantum Chemistry, Technion-Israel Institute of Technology, Haifa, 32000 (Israel)Search for more papers by this authorGraphical Abstract
How many steps? One great stride: The regio- and stereoselective carbometalation of cyclopropenyl amides and addition of an acyl silane gave polysubstituted cyclopropyl derivatives, which underwent a Brook rearrangement with inversion of configuration and selective ring cleavage when the reaction mixture was warmed to room temperature. Hydrolysis then completed the one-pot synthesis of δ-ketoamides with a quaternary stereocenter (see scheme).
Abstract
The combined regio- and stereoselective carbometalation of cyclopropenyl amides, followed by the addition of an acyl silane, led to the formation of polysubstituted cyclopropyl derivatives as unique diastereoisomers. Upon warming of the reaction mixture to room temperature, a Brook rearrangement proceeded with inversion of configuration to provide ready access to δ-ketoamides possessing a quaternary carbon center with high enantiomeric ratios through selective CC bond cleavage of the ring.
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