Palladium-catalyzed Suzuki-Miyaura coupling of thioureas or thioamides

Cross-coupling reactions involving metal carbene intermediates play an increasingly important role in C-C bond formation. Expanding the carbene precursors to a broader range of starting materials and more diverse products is an ongoing challenge in synthetic organic chemistry. Herein, we report a Su...

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Bibliographic Details
Published in:	Nature communications 2019-12, Vol.10 (1), p.5709-12, Article 5709
Main Authors:	Mai, Shaoyu, Li, Wendong, Li, Xue, Zhao, Yingwei, Song, Qiuling
Format:	Article
Language:	eng
Subjects:	Chemical bonds Construction methods Cross coupling Ketones Palladium Salts Thioureas
Online Access:	Get full text
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Summary:	Cross-coupling reactions involving metal carbene intermediates play an increasingly important role in C-C bond formation. Expanding the carbene precursors to a broader range of starting materials and more diverse products is an ongoing challenge in synthetic organic chemistry. Herein, we report a Suzuki-Miyaura coupling reaction of in situ-generated Pd-carbene complexes via desulfurization of thioureas or thioamides. This strategy enables the preparation of a broad array of substituted amidinium salts and unsymmetrical diaryl ketones. The reaction is readily scalable, compatible with bromo groups on aromatic rings, tolerant to moisture and air and has a broad substrate scope. Furthermore, a single crystal structure of Pd-diaminocarbene complex is obtained and proven to be the key intermediate in both catalytic and stoichiometric reactions. Preliminary mechanistic studies demonstrate the dual role of the silver salt as a desulfurating reagent assisting the elimination of sulfur and as oxidant facilitating the Pd /Pd /Pd catalytic cycle.
ISSN:	2041-1723 2041-1723