Highly Efficient and Functional‐Group‐Tolerant Catalysts for the Palladium‐Catalyzed Coupling of Aryl Chlorides with Thiols

Abstract

The cross-coupling reaction of aryl chlorides with aliphatic and aromatic thiols catalyzed by palladium complexes of the strongly binding bisphosphine CyPF-tBu ligand (1) is reported. Most of the reactions catalyzed by complexes of ligand 1 occur with turnover numbers that exceed those of previous catalysts by two orders of magnitude. The reactions occur with excellent yields, broad scope and high tolerance of functional groups. Coupling of aryl halides with thiols in the presence of low loadings of catalysts derived from other Josiphos type ligands, as well as ligands of other structural types, are also described.

Carbon–Sulfur Bond Formation of Challenging Substrates at Low Temperature by Using Pd‐PEPPSI‐IPent

“…[2] The discovery in 1978 by Migita and co-workers [3] that these NAS reactions could be catalyzed by Pd has been followed up in the last decade by the development of improved catalysts using a variety of metals to perform these sulfination reactions with better selectivity and under milder conditions. [4] While a couple of reports have disclosed a few select examples that proceed at 70 8C or lower, [5] the bulk of these catalyzed sulfinations have been done above this temperature, typically at, or in excess of 100 8C. Attempts to couple challenging substrates, which are hindered, electronically disfavored, or both, all require temperatures in excess of 100 8C to proceed.…”

Chlorophenols in organic synthesis

“…All experiments were performed with a 1:1 ratio of catalyst to ligand, 1 mmol of both starting compounds in DME (1.5 ml) for 2-5 h under the heating at 110 °C [45][46]. Thus, the cross-coupling with the formation of C-S bonds are the important reactions of the chlorine atom substitution.…”

“…Все эксперименты проводились с соотношением 1:1 катализатора к ли-ганду, с 1 ммоль обоих исходных ве-ществ в DME (1,5 мл) в течение 2-5 ч нагревания при 110 °С [45][46].…”

Recent advances in copper-catalyzed C-S cross-coupling reactions

“…5 Many other Pd based catalytic systems have also been developed, which are based on bidentate phosphines or diverse organophosphane derivatives. [6][7][8][9] But these systems have limitations since they require the preparation and use of PR 3 ligands which are not eco-friendly. Catalytic systems based on other transition metals such as nickel [10][11][12][13] , cobalt 14 and iron 15 have also been studied.…”