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Synthesis 2018; 50(09): 1796-1814
DOI: 10.1055/s-0036-1591957
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© Georg Thieme Verlag Stuttgart · New York

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

Miles Kenny
a   Department of Chemistry, Lancaster University, Lancaster, LA1 4YB, UK   Email: v.franckevicius@lancaster.ac.uk
,
Sybrin P. Schröder
b   Department of Chemistry, University of York, Heslington, York, YO10 5DD, UK
,
Nicholas J. Taylor
b   Department of Chemistry, University of York, Heslington, York, YO10 5DD, UK
,
Paula Jackson
b   Department of Chemistry, University of York, Heslington, York, YO10 5DD, UK
,
Daniel J. Kitson
a   Department of Chemistry, Lancaster University, Lancaster, LA1 4YB, UK   Email: v.franckevicius@lancaster.ac.uk
,
Vilius Franckevičius  *
a   Department of Chemistry, Lancaster University, Lancaster, LA1 4YB, UK   Email: v.franckevicius@lancaster.ac.uk
› Author AffiliationsWe gratefully acknowledge the Royal Society (RG150189, V.F.), the University of York (N.J.T. and V.F.), Lancaster University (M.K. and V.F.), the EU (Erasmus Exchange Programme to S.P.S.), and the Royal Society of Chemistry (Undergraduate Research Bursaries to P.J. and D.J.K.) for financial support.

Further Information

Publication History

Received: 15 January 2018

Accepted after revision: 20 February 2018

Publication Date:
27 March 2018 (online)

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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 pK a 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.

Key words

palladium - enantioselective catalysis - quaternary centres - propargylic electrophiles - 1,3-dicarbonyl compounds

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/s-0036-1591957.
  • Supporting Information
 

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