Synlett 2014; 25(09): 1319-1324
DOI: 10.1055/s-0033-1341054
letter
© Georg Thieme Verlag Stuttgart · New York

Self-Supported Ligands as a Platform for Catalysis: Use of a Polymeric Oxime in a Recyclable Palladacycle Precatalyst for Suzuki–Miyaura Reactions

Yun-Chin Yang
Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, P. R. of China   Fax: +852 28571586   Email: phtoy@hku.hk
,
Patrick H. Toy*
Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, P. R. of China   Fax: +852 28571586   Email: phtoy@hku.hk
› Author Affiliations
Further Information

Publication History

Received: 29 January 2014

Accepted after revision: 02 March 2014

Publication Date:
07 April 2014 (online)

Abstract

A self-supported oxime palladacycle precatalyst for ­Suzuki–Miyaura reactions was synthesized based on the polyether ether ketone architecture. This precatalyst was found to be highly efficient in Suzuki–Miyaura reactions when aryl bromides were used as substrates, but was less efficient in cross-coupling reactions when aryl chlorides were used. The polymeric palladacycle could be recovered and reused up to four times in such reactions, affording excellent yield of the desired product. The approach represents a novel strategy for generating such self-supported complexes for catalysis.

Supporting Information

 
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  • 20 Suzuki–Miyaura Reaction; General Procedure: Aryl halide 19 or 22 (1.0 mmol), phenylboronic acid (20; 1.2 mmol, 0.146 g), 18 (0.015 mmol, 0.002 g), Cs2CO3 (1.5 mmol, 0.489 g), DMF (2.5 mL), and H2O (2.5 mL) were placed in a 25 mL round-bottomed flask equipped with a magnetic stirrer. The flask was immersed in an oil bath regulated at 80 or 100 °C for the reaction time indicated in Table 1 or Table 2. After the reaction mixture was cooled to r.t., Et2O (8 mL) and H2O (8 mL) were added to the flask. The resulting mixture was vigorously stirred for 5 min, and then filtered. The solid 18 collected on the filter was washed with H2O (10 mL) and Et2O (10 mL) and then dried. The filtrate was transferred to a separation funnel and the organic phase was separated and washed with H2O (5 × 25 mL) and brine (10 mL), and then dried over MgSO4. The solvent was removed under reduced pressure and the resulting residue was analyzed by 1H and 13C NMR spectroscopy. When aryl chlorides were used as substrates, the crude products were purified by silica gel column chromatography.