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. 2018 Feb 28;140(8):2761-2764.
doi: 10.1021/jacs.7b13300. Epub 2018 Feb 20.

Enantioselective Intermolecular Pd-Catalyzed Hydroalkylation of Acyclic 1,3-Dienes with Activated Pronucleophiles

Nathan J Adamson  1 , Katherine C E Wilbur  1 , Steven J Malcolmson  1
Affiliations

Enantioselective Intermolecular Pd-Catalyzed Hydroalkylation of Acyclic 1,3-Dienes with Activated Pronucleophiles

Nathan J Adamson et al. J Am Chem Soc. .

Abstract

We report a highly enantioselective Pd-PHOX-catalyzed intermolecular hydroalkylation of acyclic 1,3-dienes. Meldrum's acid derivatives and other activated C-pronucleophiles, such as β-diketones and malononitriles, react with a variety of aryl- and alkyl-substituted dienes in ≤20 h at room temperature. The coupled products, obtained in up to 96% yield and 97.5:2.5 er, are easily transformed into useful chemical building blocks for downstream synthesis.

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Figures

Scheme 1
Scheme 1
Previous and Present Work in Intermolecular Enantioselective Hydroalkylation
Scheme 2
Scheme 2
Carbonyl Functionalization within Coupled Products aReaction at 80 °C.
Scheme 3
Scheme 3
Simultaneous Carbonyl and Olefin Derivatization within Hydroalkylation Products
See this image and copyright information in PMC

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