Synthesis of Novel Palladacycles and Their Application in Heck and Suzuki Reactions under Aerobic Conditions

Abstract

[reaction: see text] Design and synthesis of a novel family of furancarbothioamide-based palladacycles are reported herein. These palladacycles are thermally stable, not sensitive to air or moisture, and are applied effectively in the Heck reaction of aryl halides with terminal olefins and in the Suzuki reaction of aryl halides with arylboronic acids. These reactions were performed under aerobic conditions, leading to turnover numbers (TONs) up to 1 x 10(5).

σ‐Alkylpalladium Intermediates in Intramolecular Heck Reactions:Isolation and Catalytic Activity

“…Among the reactions of iodobenzene with acrylates, compound 2 b is comparable to other catalytic systems such as sulfur- [18] or rhenium-containing [19] and imine- [20] or oximederived [21] palladacycles, even if there are other systems that perform better. [22] Similar catalytic activity was shown by iodo-A C H T U N G T R E N N U N G (indolyl)palladacycles 13 a and 13 b (Table 1, entries 4 and 5).…”

“…[18] However, it should be mentioned that there are other systems with higher activity. [26] On the basis of the results obtained by using s-alkylpalladium-iodine complexes as effective precatalysts for Heck reactions, we next examined whether they could also facilitate Pd-catalyzed cross-coupling reactions.…”

Development of a Method for Preparing a Highly Reactive and Stable, Recyclable and Environmentally Benign Organopalladium Catalyst Supported on Sulfur‐Terminated Gallium Arsenide(001): A Three‐Component Catalyst, {Pd}‐S‐GaAs(001), and its Properties

“…In entries 10 and 11, aryl iodides with electron-withdrawing groups at the para-position were used to yield the corresponding products at the 1st run, however, after the 2nd run, the chemical yields decreased drastically, and no reactivity remained after the 5th run. In entry 12, 1-iodonaphthalene, which was sometimes known for its low activity, [9] was used as a substrate and gave the corresponding product in excellent yield over 10 runs and the average yield was 94 %. The fact that non-or de-activated aryl iodides react better than activated ones (entries 3 -6 versus [e] Reaction was carried out in toluene at 135 8C (bath temperature) for 24 h.…”

Biaryl synthesis using highly stablearyl[2-(hydroxymethyl)phenyl]dimethylsilanes and aryl iodides under fluoride-free conditions

“…It is worth noting that t-BuMe 2 Si-ether, which is easily cleaved under the conventional fluoride activation protocols, survives completely (entry 12). Ortho-substituted aryl iodides cross-coupled with 1a in good to excellent yields, irrespective of electronic nature and number of the substituents (entries [13][14][15][16][17][18][19]. Heteroaryl groups such as pyridyl, pyradyl, and thienyl were also introduced successfully to give heterobiaryl compounds (entries 20-24).…”