Use of Carbonyldiimidazole as an Activator of Formic Acid in a Tris(dibenzylideneacetone)dipalladium-Catalyzed Formylation of Aryl Iodides

Sundar Nadhagopal; Zulelal Dolas; Arundutt Silamkoti; Anuradha Gupta; Arvind Mathur; Sukhen Karmakar

doi:10.1055/a-2047-9575

Synlett, Table of Contents

Synlett 2023; 34(15): 1809-1813
DOI: 10.1055/a-2047-9575

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Use of Carbonyldiimidazole as an Activator of Formic Acid in a Tris(dibenzylideneacetone)dipalladium-Catalyzed Formylation of Aryl Iodides

Sundar Nadhagopal

^aDepartment of Discovery Synthesis, Biocon Bristol Myers Squibb Research Center (BBRC), Biocon Park, Bommasandra IV Phase, Jigani Link Road, Bangalore 560 099, India

,

Zulelal Dolas

^aDepartment of Discovery Synthesis, Biocon Bristol Myers Squibb Research Center (BBRC), Biocon Park, Bommasandra IV Phase, Jigani Link Road, Bangalore 560 099, India

,

Arundutt Silamkoti

^aDepartment of Discovery Synthesis, Biocon Bristol Myers Squibb Research Center (BBRC), Biocon Park, Bommasandra IV Phase, Jigani Link Road, Bangalore 560 099, India

,

Anuradha Gupta

^aDepartment of Discovery Synthesis, Biocon Bristol Myers Squibb Research Center (BBRC), Biocon Park, Bommasandra IV Phase, Jigani Link Road, Bangalore 560 099, India

,

Arvind Mathur

^bSmall Molecule Drug Discovery, Research and Early Development, Bristol Myers Squibb, P.O. Box 4000, Princeton, New Jersey 08543-4000, USA

,

Sukhen Karmakar∗

^aDepartment of Discovery Synthesis, Biocon Bristol Myers Squibb Research Center (BBRC), Biocon Park, Bommasandra IV Phase, Jigani Link Road, Bangalore 560 099, India

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Abstract

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Abstract

A carbonyldiimidazole (CDI)-promoted generation of CO from formic acid has been exploited in a reductive formylation of aryl iodides in the presence of tris(dibenzylideneacetone)dipalladium. The reaction conditions are mild with a broad functional-group tolerance that includes keto, bromo, nitrile, ester, and nitro groups. In the reaction pathway, CDI reacts with formic acid to generate a formyl imidazole that ultimately produces the CO needed for the formylation process on the activated arylpalladium complex.

Key words

formylation - carbonyldiimidazole - formic acid - palladium catalysis - aryl aldehydes - aryl iodides

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References

References and Notes

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19 4-Methoxybenzaldehyde (2); Typical Procedure [CAS Reg. No. 123–11–5] HCO₂H (207 mg, 4.5 mmol) was added to a solution of CDI (389 mg, 2.4 mmol) in DMF (5 mL) at rt and the mixture was stirred for 2 h. 4-iodoanisole (1; 236 mg, 1.0 mmol), Et₃N (253 mg, 2.5 mmol), and Pd₂(dba)₃ (46 mg, 0.05 mmol, 5.0 mol%) were added successively and the mixture was heated at 70 °C for 6 h (monitored by TLC). The mixture was cooled to rt, diluted with H₂O (5 mL), and extracted with MTBE (2 × 15 mL). The combined organic layer was washed with H₂O (10 mL) and brine (10 mL), then dried (Na₂SO₄) and concentrated. The residue was purified by flash column chromatography [silica gel, PE–EtOAc (20:1)] to give a colorless liquid; yield: 122 mg (91%). ¹H NMR (400 MHz, CDCl₃): δ = 9.83 (s, 1 H), 7.82–7.75 (d, J = 8.6 Hz, 2 H), 7.01–6.84 (d, J = 8.6 Hz, 2 H), 3.83 (s, 3 H). ¹³C NMR (101 MHz, CDCl₃): δ = 189.59, 163.45, 130.78, 128.80, 113.15, 54.40. The characterization data for this compound were identical to those previously reported in the literature.⁴

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