Formation of Carbon Quaternary Stereogenic Center in Acyclic Systems via a Sequence of Carbometalation–Intramolecular Cyclization–Silicon Activation

Maya Preshel-Zlatsin; Fa-Guang Zhang; Guillaume Eppe; Ilan Marek

doi:10.1055/s-0035-1561666

Synthesis, Table of Contents

Synthesis 2016; 48(19): 3279-3286
DOI: 10.1055/s-0035-1561666

paper

Formation of Carbon Quaternary Stereogenic Center in Acyclic Systems via a Sequence of Carbometalation–Intramolecular Cyclization–Silicon Activation

Maya Preshel-Zlatsin

The Mallat Family Laboratory of Organic Chemistry, Schulich Faculty of Chemistry and The Lise Meitner-Minerva Center for Computational Quantum Chemistry, Technion-Israel Institute of Technology, Technion City, Haifa 32000, Israel Email: chilanm@tx.technion.ac.il

,

Fa-Guang Zhang

The Mallat Family Laboratory of Organic Chemistry, Schulich Faculty of Chemistry and The Lise Meitner-Minerva Center for Computational Quantum Chemistry, Technion-Israel Institute of Technology, Technion City, Haifa 32000, Israel Email: chilanm@tx.technion.ac.il

,

Guillaume Eppe

The Mallat Family Laboratory of Organic Chemistry, Schulich Faculty of Chemistry and The Lise Meitner-Minerva Center for Computational Quantum Chemistry, Technion-Israel Institute of Technology, Technion City, Haifa 32000, Israel Email: chilanm@tx.technion.ac.il

,

Ilan Marek*

The Mallat Family Laboratory of Organic Chemistry, Schulich Faculty of Chemistry and The Lise Meitner-Minerva Center for Computational Quantum Chemistry, Technion-Israel Institute of Technology, Technion City, Haifa 32000, Israel Email: chilanm@tx.technion.ac.il

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Abstract

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Dedicated to the memory of Jean Normant, a wonderful teacher and truly inspirational colleague

Abstract

The diastereoselective carbometalation reaction of cyclopropenyl esters followed by reaction with acylsilanes provides γ-silylated lactones that undergo a ‘sila-Grob’ fragmentation to give pyrone enolates as a new source of acyclic δ-diketones, δ-keto acid, and δ-keto ester derivatives possessing a quaternary stereocenter.

Key words

quaternary carbon stereocenters - carbometalation - cyclopropenes - silicon activation - fragmentation

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References

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