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. 2017 Dec 22;23(72):18282-18288.
doi: 10.1002/chem.201704442. Epub 2017 Nov 30.

Auto-Tandem Catalysis: PdII -Catalysed Dehydrogenation/Oxidative Heck Reaction of Cyclopentane-1,3-diones

Claire J C Lamb  1 , Bryan G Nderitu  1 , Gemma McMurdo  1 , John M Tobin  1 , Filipe Vilela  1 , Ai-Lan Lee  1
Affiliations

Auto-Tandem Catalysis: PdII -Catalysed Dehydrogenation/Oxidative Heck Reaction of Cyclopentane-1,3-diones

Claire J C Lamb et al. Chemistry. .

Abstract

A PdII catalyst system has been used to successfully catalyse two mechanistically distinct reactions in a one-pot procedure: dehydrogenation of 2,2-disubstituted cyclopentane-1,3-diones and the subsequent oxidative Heck coupling. This auto-tandem catalytic reaction is applicable to both batch and continuous flow processes, with the latter being the first example of a tandem aerobic dehydrogenation/oxidative Heck in flow. In addition, a telescoped reaction involving enantioselective desymmetrisation of the all-C quaternary centre was successfully achieved.

Keywords: aerobic oxidation; auto-tandem catalysis; one-pot synthesis; oxidative Heck; palladium.

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Figures

Figure 1
Figure 1
Examples of natural products containing the 2,2‐disubstituted cyclopentene‐1.3‐dione core.
Scheme 1
Scheme 1
(A) Previous oxidative Heck desymmetrisation; (B) stoichiometric oxidant method towards 1; (C) Stahl's aerobic oxidation; (D) this work.
Scheme 2
Scheme 2
Initial attempts at the one‐pot reaction led to inconsistent results.
Scheme 3
Scheme 3
Increasing ligand:Pd ratio significantly improves reproducibility of oxidation step.
Scheme 4
Scheme 4
Optimised one‐pot dehydrogenation/oxidative Heck reaction.
Scheme 5
Scheme 5
Tandem dehydrogenation/oxidative Heck under continuous flow conditions.
Scheme 6
Scheme 6
Enantioselective dehydrogenation/oxidative Heck reactions.
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