Rights statement: © Copyright 2018, Thieme Medical Publishers, Inc. All Rights Reserved
Accepted author manuscript, 10.9 MB, PDF document
Available under license: CC BY-NC: Creative Commons Attribution-NonCommercial 4.0 International License
Final published version
Research output: Contribution to Journal/Magazine › Journal article › peer-review
Research output: Contribution to Journal/Magazine › Journal article › peer-review
}
TY - JOUR
T1 - Palladium-Catalysed Construction of All-Carbon Quaternary Centres with Propargylic Electrophiles
T2 - Challenges in the Simultaneous Control of Regio-, Chemo- and Enantioselectivity
AU - Kenny, Miles
AU - Schröder, Sybrin
AU - Taylor, Nicholas
AU - Jackson, Paula
AU - Kitson, Daniel
AU - Franckevicius, Vilius
N1 - © Copyright 2018, Thieme Medical Publishers, Inc. All Rights Reserved
PY - 2018/5
Y1 - 2018/5
N2 - This article describes the palladium-catalysed three-component coupling of 1,3-dicarbonyl compounds with nucleophiles and propargylic electrophiles for the generation of quaternary all-carbon centres in a single step, which necessitates the simultaneous control of regio-, chemo- and enantioselectivity. The use of propargyl enol carbonates, the source of two of the components, was found to be essential in maintaining high levels of regiocontrol and chemoselectivity, whereas a careful analysis of pKa trends of O-, C- and N-nucleophiles as the other coupling partner indicates that the highest levels of selectivity are likely to be obtained with relatively acidic species, such as phenols, 1,3-dicarbonyl compounds and aromatic N-heterocycles. Finally, studies towards the development of the catalytic enantioselective construction of quaternary all-carbon centres by means of alkenylation and allylic alkylation are disclosed.
AB - This article describes the palladium-catalysed three-component coupling of 1,3-dicarbonyl compounds with nucleophiles and propargylic electrophiles for the generation of quaternary all-carbon centres in a single step, which necessitates the simultaneous control of regio-, chemo- and enantioselectivity. The use of propargyl enol carbonates, the source of two of the components, was found to be essential in maintaining high levels of regiocontrol and chemoselectivity, whereas a careful analysis of pKa trends of O-, C- and N-nucleophiles as the other coupling partner indicates that the highest levels of selectivity are likely to be obtained with relatively acidic species, such as phenols, 1,3-dicarbonyl compounds and aromatic N-heterocycles. Finally, studies towards the development of the catalytic enantioselective construction of quaternary all-carbon centres by means of alkenylation and allylic alkylation are disclosed.
KW - PALLADIUM
KW - enantioselective catalysis
KW - quaternary centres
KW - propargylic electrophiles
KW - 1,3-dicarbonyl compounds
U2 - 10.1055/s-0036-1591957
DO - 10.1055/s-0036-1591957
M3 - Journal article
VL - 50
SP - 1796
EP - 1814
JO - SYNTHESIS
JF - SYNTHESIS
SN - 0039-7881
IS - 9
ER -