Catalytic α-Arylation of Ketones with Heteroaromatic Esters

Published as part of the Cluster C–O Activation

Abstract

Heteroaromatic esters were found to be applicable as an arylating agent for the Pd-catalyzed α-arylation of ketones in a decarbonylative fashion. The use of our in-house ligand, dcypt, enabled this unique bond formation. Considering the ubiquity and low cost of ­aromatic esters, the present work will allow for rapid access to valuable α-aryl carbonyl compounds.

Key words

α-arylation - aromatic esters - decarbonylative coupling - palladium - heteroarenes - ketones

• References and Notes


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• 19 Representative Experimental Procedure for Catalytic Decarbonylative α-Arylation of Ketones with Aromatic Esters A 20 mL glass vessel equipped with J. Young^® O-ring tap containing a magnetic stirring bar and CsF (121.5 mg, 0.80 mmol, 2.0 equiv) was dried with a heatgun in vacuo and filled with N₂ gas after cooling to room temperature. To this vessel were added aromatic phenyl ester 1A (130.2 mg, 0.40 mmol, 1.0 equiv), aryl ketones 2 (120.1 mg, 0.80 mmol, 2.0 equiv), Pd(OAc)₂ (4.49 mg, 0.020 mmol, 5.0 mol%), and dcypt (19.1 mg, 0.040 mmol, 10 mol%). The vessel was vacuumed and refilled N₂ gas three times. To this was added toluene (1.6 mL). The vessel was sealed with O-ring tap and then heated at 150 °C for 18 h in a 9-well aluminum reaction block with stirring. After cooling the reaction mixture to room temperature, the mixture was passed through a short silica gel pad with EtOAc as an eluent. The filtrate was concentrated and the residue was purified by Isolera^® (hexane/EtOAc = 5:1) afforded 3Aa as a white solid (97.5 mg, 69% yield). Compound 3Aa: ¹H NMR (400 MHz, CDCl₃): δ = 8.20 (d, J = 8.8 Hz, 1 H), 8.11 (d, J = 8.8 Hz, 2 H), 8.04 (d, J = 8.8 Hz, 2 H), 7.86 (d, J = 8.8 Hz, 1 H), 7.73–7.67 (m, 2 H), 7.53–7.41 (m, 4 H), 6.95 (d, J = 8.8 Hz, 2 H), 4.71 (s, 2 H), 3.86 (s, 3 H). ¹³C NMR (101 MHz, CDCl₃): δ = 194.7, 163.9, 157.0, 148.5, 142.0, 139.5, 130.8, 130.5, 129.4, 129.3, 129.2, 128.7, 127.5, 126.7, 126.5, 123.5, 120.7, 114.0, 55.5, 42.1. ESI-HRMS: m/z calcd for C₂₄H₂₀NO₂ [M + H]⁺: 354.1489; found: 354.1487.