Synlett 2018; 29(05): 650-654
DOI: 10.1055/s-0036-1589143
letter
© Georg Thieme Verlag Stuttgart · New York

Cyrene as a Bio-Based Solvent for the Suzuki–Miyaura Cross-Coupling

Kirsty L. Wilson
a  Department of Pure and Applied Chemistry, University of Strathclyde, Thomas Graham Building, 295 Cathedral Street, Glasgow, G1 1XL, UK   Email: allan.watson.100@strath.ac.uk
,
Jane Murray
b  Merck KgaA, Frankfurter Straße 250, 64293 Darmstadt, Germany
,
Craig Jamieson
a  Department of Pure and Applied Chemistry, University of Strathclyde, Thomas Graham Building, 295 Cathedral Street, Glasgow, G1 1XL, UK   Email: allan.watson.100@strath.ac.uk
,
a  Department of Pure and Applied Chemistry, University of Strathclyde, Thomas Graham Building, 295 Cathedral Street, Glasgow, G1 1XL, UK   Email: allan.watson.100@strath.ac.uk
› Author Affiliations
We thank the University of Strathclyde for a PhD studentship (KLW) and Merck KGaA for financial and material support.
Further Information

Publication History

Received: 10 October 2017

Accepted after revision: 02 November 2017

Publication Date:
11 December 2017 (online)

Abstract

The Suzuki–Miyaura (SM) cross-coupling is the most broadly utilized Pd-catalyzed C–C bond-forming reaction in the chemical industry. A large proportion of SM couplings employ dipolar aprotic solvents; however, current sustainability initiatives and increasingly stringent regulations advocate the use of alternatives that exhibit more desirable properties. Here we describe the scope and utility of the bio-derived solvent Cyrene™ in SM cross-couplings and evaluate its suitability as a reaction medium for this benchmark transformation from discovery to gram scale.

Supporting Information

 
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  • 64 General Procedure for Suzuki–Miyaura Coupling in Cyrene To an oven dried 5 mL microwave vessel was added Pd(dppf)Cl2·CH2Cl2 (4 mol%), halide/pseudohalide (1 equiv), boron coupling partner (1 equiv), and Cs2CO3 (3 equiv). The vessel was then capped and purged with N2 before addition of Cyrene (1 mL, 0.25 M) and H2O (1.8 mL). The reaction mixture was heated to 50 °C and maintained at this temperature with stirring for 5 h before the vessel was vented and decapped. The solution was then diluted with Et2O (10 mL) and washed with water (2 × 20 mL) and brine (2 × 20 mL). The organics were then passed through a hydrophobic frit and concentrated under reduced pressure to give a residue, which was purified by flash chromatography (silica gel) to afford the title compound. 4-Phenyltoluene (4a) Prepared according to the General Procedure using Pd(dppf)Cl2·CH2Cl2 (8.2 mg, 0.01 mmol, 4 mol%), bromotoluene 2a (42.8 mg, 0.25 mmol, 1 equiv), phenylboronic acid (3a, 30.5 mg, 0.25 mmol, 1 equiv), Cs2CO3 (244.5 mg, 0.75 mmol, 3 equiv), Cyrene (1 mL, 0.25 M), and H2O (1.8 mL, 400 equiv). After 5 h, the reaction mixture was subjected to the purification method outlined in the General Procedure (silica gel, 0–5% Et2O in PE) to afford the title compound as a white solid (42.9 mg, quant). 1H NMR (CDCl3, 400 MHz): δ = 7.62 (dd, J = 8.3, 1.2 Hz, 2 H), 7.53 (d, J = 8.1 Hz, 2 H), 7.46 (t, J = 7.6 Hz, 2 H), 7.38–7.33 (m, 1 H), 7.29 (d, J = 7.9 Hz, 2 H), 2.43 (s, 3 H). 13C NMR (CDCl3, 101 MHz): δ = 141.2, 138.4, 136.9, 129.5, 128.7, 126.9, 21.1.