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. 2016 Apr 20;138(15):5016-9.
doi: 10.1021/jacs.6b01533. Epub 2016 Apr 11.

Decarboxylative Cross-Electrophile Coupling of N-Hydroxyphthalimide Esters with Aryl Iodides

Kierra M M Huihui  1 , Jill A Caputo  1 , Zulema Melchor  1 , Astrid M Olivares  1 , Amanda M Spiewak  1 , Keywan A Johnson  1 , Tarah A DiBenedetto  1 , Seoyoung Kim  1 , Laura K G Ackerman  1 , Daniel J Weix  1
Affiliations

Decarboxylative Cross-Electrophile Coupling of N-Hydroxyphthalimide Esters with Aryl Iodides

Kierra M M Huihui et al. J Am Chem Soc. .

Abstract

A new method for the decarboxylative coupling of alkyl N-hydroxyphthalimide esters (NHP esters) with aryl iodides is presented. In contrast to previous studies that form alkyl radicals from carboxylic acid derivatives, no photocatalyst, light, or arylmetal reagent is needed, only nickel and a reducing agent (Zn). Methyl, primary, and secondary alkyl groups can all be coupled in good yield (77% ave yield). One coupling with an acid chloride is also presented. Stoichiometric reactions of (dtbbpy)Ni(2-tolyl)I with an NHP ester show for the first time that arylnickel(II) complexes can directly react with NHP esters to form alkylated arenes.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Scheme 1
Scheme 1. Conversion of Alkanoic Acids to Radicals
Reactions run with 10 mol % of (dtbbpy)NiBr2 and Zn0 (2 equiv) in DMA (0.8 M) for 20 h. dtbbpy = 4,4′-di-tert-butyl-2,2′-bipyridine. GC yield, uncorrected. N-Hydroxysuccinimide ester of 4-phenyl butanoic acid was used in place of NHP ester 1a, along with 20 mol % DMAP.
Scheme 2
Scheme 2. Coupling of Alkyl NHP Esters with ArI
Reactions were run on 0.8 mmol scale in 1 mL of DMA. Yields are after isolation and purification. See Supporting Information. Reaction was set up on the benchtop in a round-bottom flask. 12 mol % of catalyst was used on a 0.4 mmol scale reaction. Yield of 3e adjusted to account for 4 wt % N-Boc pyrrolidine in sample. Yield of 3m adjusted to account for 14 wt % of phthalimide and diisopropyl urea that we were unable to separate by chromatography.
See this image and copyright information in PMC

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