Polymer incarcerated metals

In 2015, Kobayashi and co-workers reported a PI/CB-Au/Pd (PI/CB, polymer-incarcerated metal nanoparticle catalyst with carbon black as a secondary supporter) complex-catalyzed IV-alkylatiou of amides with alcohols (Eq. 51) [169]. The catalyst could be reused 11 times without appreciable loss of catalytic activity (1st, 99 % lllh, 95 %). 

Alternative cocatalysts, such as [Fe(pc)]20 (pc = phthalocyanine) and AIBN, have also been reported for catalytic aerobic DDQ oxidation reactions, though these have seen less widespread application than NO [28]. Aerobic quinone-catalyzed dehydrogenation reactions using less oxidizing quinones, such as chloranil, have been reported using polymer-incarcerated noble metal catalysts reported by Kobayashi and colleagues [29, 30]. 

Lewis acids can be immobilized to polymers by means of covalent bonding, ionic bonding, or coordination of polymeric ligand to Lewis acidic metal species. Besides these classical methods, microencapsulation and polymer incarcerated (PI) methods have been developed. In most cases, Lewis acids were immobilized as a pendant group of the polymer chain. Main-chain Lewis acid polymers have... 

Kobayashi and coworkers further developed a new immobilizing technique for metal catalysts, a PI method [58-61]. They originally used the technique for palladium catalysts, and then applied it to Lewis acids. The PI method was successfully used for the preparation of immobilized Sc(OTf)3. When copolymer (122) was used for the microencapsulation of Sc(OTf)3, remarkable solvent effects were observed. Random aggregation of copolymer (122)-Sc(OTf)3 was obtained in toluene, which was named as polymer incarcerated (PI) Sc(OTf)3. On the other hand, spherical micelles were formed in THF-cyclohexane, which was named polymer-micelle incarcerated (PMI) Sc(OTf)3.. PMI Sc(OTf)3 worked well in the Mukaiyama-aldol reaction of benzaldehyde with (123) and showed higher catalytic activity compared to that of PI Sc(OTf)3 mainly due to its larger surface area of PMI Sc(OTf)3. This catalyst was also used in other reactions such as Mannich-type (123) and (125) and Michael (127) and (128) reactions. For Michael reactions, inorganic support such as montmorilonite-enwrapped Scandium is also an efficient catalyst [62]. 

Entrapment or intercalation of metal species in pores and cavities of solid supports has frequently been used for the immobilization of catalysts in inorganic materials such as zeolites, clays, charcoals, silicas, aluminas, and other solids. Though this review article focuses on the immobilization of palladium complexes on polymer supports via covalent and/or coordination bonds, recent novel approaches to polymer-supported palladium species (including palladium nanoparticles) via nonbonding immobilization, such as encapsulation and incarceration, are intriguing because of their high potential for utility. In this section, several representatives are introduced. 

Various oxidations with [bis(acyloxy)iodo]arenes are also effectively catalyzed by transition metal salts and complexes [726]. (Diacetoxyiodo)benzene is occasionally used instead of iodosylbenzene as the terminal oxidant in biomimetic oxygenations catalyzed by metalloporphyrins and other transition metal complexes [727-729]. Primary and secondary alcohols can be selectively oxidized to the corresponding carbonyl compounds by PhI(OAc)2 in the presence of transition metal catalysts, such as RuCls [730-732], Ru(Pybox)(Pydic) complex [733], polymer-micelle incarcerated ruthenium catalysts [734], chiral-Mn(salen)-complexes [735,736], Mn(TPP)CN/Im catalytic system [737] and (salen)Cr(III) complexes [738]. The epox-idation of alkenes, such as stilbenes, indene and 1-methylcyclohexene, using (diacetoxyiodo)benzene in the presence of chiral binaphthyl ruthenium(III) catalysts (5 mol%) has also been reported however, the enantioselectivity of this reaction was low (4% ee) [739]. 

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