Palladium-Catalysed Construction of All-Carbon Quaternary Centres with Propargylic Electrophiles:Challenges in the Simultaneous Control of Regio-, Chemo- and Enantioselectivity

Kenny, Miles and Schröder, Sybrin and Taylor, Nicholas and Jackson, Paula and Kitson, Daniel and Franckevicius, Vilius (2018) Palladium-Catalysed Construction of All-Carbon Quaternary Centres with Propargylic Electrophiles:Challenges in the Simultaneous Control of Regio-, Chemo- and Enantioselectivity. SYNTHESIS, 50 (9). pp. 1796-1814. ISSN 0039-7881

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Abstract

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.

Item Type:
Journal Article
Journal or Publication Title:
SYNTHESIS
Additional Information:
© Copyright 2018, Thieme Medical Publishers, Inc. All Rights Reserved
Uncontrolled Keywords:
/dk/atira/pure/subjectarea/aacsb/disciplinebasedresearch
Subjects:
ID Code:
124283
Deposited By:
Deposited On:
28 Mar 2018 08:58
Refereed?:
Yes
Published?:
Published
Last Modified:
25 Sep 2020 03:36