trans-Dichlorobis(XPhos)palladium(II) Precatalyst for Suzuki–Miyaura Cross-Coupling Reactions of Aryl/Vinyl Sulfonates/Halides: Scope, Mechanistic Study, and Synthetic Applications

Abstract

Suzuki–Miyaura cross-coupling reactions of aryl/vinyl sulfonates/halides with various boron species were performed using an easily available trans -dichlorobis(XPhos)palladium(II) precatalyst. Under microwave assistance, more than 30 coupling products were obtained with yields ranging from 23 to 99%, including the synthesis of two bioactive compounds, dubamine and tamoxifen. A mechanistic investigation of the Suzuki–Miyaura reaction was conducted notably by nuclear magnetic resonance (NMR) and high-resolution mass spectroscopy, revealing the nature of the active Pd 0 species and of the reducing entity.

Homogeneous and Recyclable Palladium Catalysts: Application in Suzuki–Miyaura Cross-Coupling Reactions

“…After consideration of the reaction time, solvent employed, and temperature, we selected L1 , THF, and room temperature as perfectly cromulent reaction conditions. Our catalytic conditions are comparable in performance to other well-established Suzuki–Miyaura protocols employing PdCl 2 (dppf), although much lower loadings are possible employing current state-of-the-art methodology. − …”

Rhazinilam–leuconolam family of natural products: a half century of total synthesis

“…Suzuki coupling of the latter with 2-aminophenylboronic acid under microwave irradiation (30 min) using PdCl 2 (XPhos) 2 precatalyst furnished the aryl-pyrrole 89 in 87% yield. 65 Saponification and immediate macrolactamization in the presence of Mukaiyama's reagent provided the 13-membered lactam 90 in 87% yield. The synthesis of (±)-rhazinilam was completed by a regioselective intramolecular oxidative Heck coupling and subsequent hydrogenation of the resulting vinyl chain.…”

Recent Advances in Microwave‐assisted Cross‐Coupling Reactions

“…Very recently, Blanc group [49] reported a Suzuki‐Miyaura cross‐coupling reaction of aryl boronic acids 14 with various aryl sulfonates and halides 13 using 5 mol% of PdCl 2 (XPhos) 2 as catalyst in butanol under microwave irradiation (Scheme 33). However, as mentioned by the authors, 1 equiv.…”