Heck-Matsuda reaction arylation

The use of arenediazonium salts as arylating reagents of olefins was first reported by Matsuda in 1977 [18,19]. This reaction has been appropriately coined the Heck-Matsuda reaction (Scheme 1.4a). 

Arylations with the Heck-Matsuda Reaction - Recent Developments... 

In 2012, Gholinejad reported the Heck-Matsuda reaction (as well as the Suzuki-Miyaura reaction) using palladium nanoparticles [97]. The nanoparticles were supported on agarose beads, and at a loading of 2.6 pmol a variety of aryl ditizonium tetrafluoroborate salts could be coupled with... 

Heck-Matsuda reaction. This reaction was first described in 1977 by Tsutomu Matsuda, who pointed out the unique reactivity of the arenediazonium salts in the Heck reaction, allowing a fast and direct generation of cationic aryl-palladium species in the reaction medium. Indeed, the high levels of chemo- and stereocontrol observed in these reactions usually do not depend on the use of halide scavengers (such Ag" or Tl salts), dry solvents, inert atmosphere, or phosphane hgands (Scheme 1) ... 

Another aspect that probably contributed to the limited interest in the Heck-Matsuda reaction in organic synthesis for many years was the absence of its enantioselective version. In 2012, we described the first enantioselective Heck-Matsuda arylation of olefins using the chiral bisoxazoline 1 as the ligand for this transformation. This opened the door for the application of this reaction in more challenging transformations such as the enantioselective arylation of acyclic olefins in good yields with enantiocontrol (Scheme 2). Initial studies were carried out aiming at the desymmetrization of cyclic olefins (2), and arylation of more challenging acyclic olefins (4). 

We reported our first results with the Heck-Matsuda reaction in the late 1990s for the arylation of chiral, nonracemic, endocyclic enecarbamates 9 to produce the aryl pyrroUdines 8. These interesting intermediates were further applied in the total synthesis of several fully substituted A -heterocycles with pharmacologically active compounds such as the antibiotic and hypertensive pyrrolidine alkaloid codonopsinine 6, and the antitrypanosomal Schramm s C-azanucleoside 7 (Scheme 4). ... 

The initial objective in these early studies was the synthesis of the trans-substituted aryl pyrrolidines. Therefore, the Heck-Matsuda reactions were... 

This methodology was also applied to the stereoselective arylation of substituted cyclic compounds to provide highly complex aryl-substituted cyclo-pentene scaffolds with total control of the double bond position. This unique substrate-directed Heck-Matsuda reaction was applied in the total synthesis of the SlPi agonist VPC01091 (130). 

Diazonium salts are very useful starting materials for Heck reactions and other cross-coupling reactions (see 4.2.2). The first protocols have been developed by Matsuda and colleagues, and the reaction sometimes is being called Heck-Matsuda reaction. Since the 1970 s, a number of applications have emerged. Moro et al. used an arenediazonium salt in a Heck arylation reaction to obtain the resulting trans-stilbene derivative in excellent yield with complete stereocontrol (Scheme 5-18). ... 

It should be mentioned that O-methylation of the ketone in 24 was necessary to avoid competition between the Heck-Matsuda arylation and the nucleophilic addition of the enol to the aryldiazonium salt, a process known as the Japp-Klingemann reaction. Indeed, when 24 was submitted to the standard Heck-Matsuda reacticm conditions, the azo compound 25 was obtained in quantitative yield (Scheme 9). Azo compounds are easily detected due to the formation of highly colored products via this reaction. 

The Matsuda-Heck reaction of an aryl diazonium salt 82 with 1,1,1-trifluoropropene... 

One of the first examples of a Pd-catalyzed coupling reaction realized on an industrial scale is the Matsuda-Heck reaction of an aryl diazonium salt with 1,1,1-trifluoropropene developed by Baumeister and co-workers at Ciba-Geigy and today performed on ton scale by Novartis for the synthesis of a sulfonylurea herbicide (Prosulfuron). By combining three synthetic steps (diazotization, aUcenylation, and hydrogenation) in a... 

A detailed reaction proving the nucleophilic attack was shown for platinum complexes [25]. The aUcoxide coordinated to platinum attacks phosphorus while the carbon atom coordinated to platinum migrates to phosphorus. Thermodynamically the result seems more favorable, but mechanistically this shuffle remains mysterious (see Figure 8). Coordination to platinum makes the phosphorus atom more susceptible to nucleophilic attack, and the harder atoms (P and O) and softer ones (C and Pt) recombine as one might expect. The same mechanism was proposed by Matsuda [22] for the decomposition of triphenylphoshine by palladium(II) acetate. In this study the aryl phosphines are used as a source for aryl groups that are converted into stilbenes via a Heck reaction. Even alkyl phosphines underwent P-C bond cleavage via palladium acetate. 

This represents the first ESI-MS complete study of Matsuda-Heck arylation with aryldiazonium salts and allowed the authors to propose a detailed catalytic cycle for this reaction, outlined in Scheme 7.11. The main cationic intermediates of this catalytic cycle were detected and structurally characterized directly from the reaction mixture. 

---