Silver sequestration of halides for the activation of Pd(OAc)₂ catalyzed Mizoroki‐Heck reaction of 1,1 and 1,2 ‐ Disubstituted alkenes

Abstract

A ligand free catalytic system consisting of Pd(OAc)2 (cat) and stoichiometric quantities of silver salts, AgOAc or AgBF4, exhibit high efficiency in the Mizoroki‐Heck arylation, transforming aryl iodides and 1,1 as well as 1,2 disubstituted alkenes into 1,1,2 – trisubstituted aryl alkenes in excellent yields in very short reaction times.

Benign Arylations of Dimethyl Itaconate via Heck–Matsuda Reaction Utilizing in‐Situ Generated Palladium on Aluminum Oxide

“…Dimethyl ( E )‐2‐(4‐Methoxybenzylidene) Succinate (3a): Pale yellow oil (2.51 g, 95 %); 1 H NMR (400 MHz, CDCl 3 ): δ = 7.85 (s, 1H), 7.33 (d, J = 8.7 Hz, 2H), 6.92 (d, J = 8.8 Hz, 2H), 3.83 (s, 3H), 3.82 (s, 3H), 3.74 (s, 3H), 3.58 (s, 2H); 13 C NMR (101 MHz, CDCl 3 ): δ = 171.7, 168.0, 160.2, 141.8, 130.9, 127.3, 123.7, 114.1, 55.3, 52.2, 52.1, 33.5; HRMS (ESI TOF): calcd. for C 14 H 17 O 5 [M + H] + 265.1078, found 265.1074.…”

“…Furthermore, the use of amines as bases and DMF as an ecologically problematic solvent was necessary. For exhibiting the efficiency of the synthesis of arylmethylidene succinates via Mizoroki–Heck reaction, Iyer et al described very recently a ligand free catalytic system consisting of Pd(OAc) 2 and stoichiometric quantities of silver salts as sequestration agents for halides . Despite the good results, the use of phosphines, bases and/or silver salts is indispensable for the synthetic protocols mentioned above.…”

Mechanistic aspects of the Pd(OAc)n (n = 1–3) catalyzed ethylene acetoxylation: A density functional theory study

“…[12] Similarly, a USI-type heterogeneous catalyst (Pd-Pt-HOAc/Al 2 O 3 ) was developed for the production of vinyl acetate. [13] In recent years, homogenous and non-corrosive palladium acetate has been applied to various reactions, including cyclometalation, [14] isomerization, [15] aromatic substitution, [16] coupling reaction, [17,18] and acetoxylation. For palladium-catalyzed sp 2 C-H acetoxylation, Wang et al [19] investigated the palladium-catalyzed ortho C-H acetoxylation of 2-arylindazoles with phenyliodine (III) diacetate as the acetoxy source.…”

Noncatalytic Bromination of Icosahedral Dicarboranes: The Key Role of Anionic Bromine Clusters Facilitating Br Atom Insertion into the B–H σ-Bond

“…Practical interest in B-halogenated carboranes has remained limited because of the reduced reactivity of the halogen atom . Recently, however, techniques have been developed that allow the creation of B–N and B–C bonds by cross-coupling according to the reactions of Kumada, , Suzuki, − and Heck − (see also refs and ). This approach opens up opportunities for the synthesis of new compounds with useful properties, including biologically active compounds. ,, …”