Transfer microwave-assisted

In 2003, Van der Fycken pubhshed a copper- and palladiirm-free microwave-assisted Sonogashira-type protocol in water with phenylacetylene as the alkyne (Scheme 51) [69]. The phase-transfer agent TBAB was used to facilitate... 

Recently it has been shown that the microwave-assisted decoration of the 2(lff)-pyrazinone scaffold can allow an easy introduction of different substituents at the C-3 and even to the less reactive C-5 position [29]. Taking full advantage of combinatorial principles, some of these pathways were transferred to microwave-enhanced solid-phase chemistry, opening the way for the generation of many biologically interesting structures [108]. 

Several microwave-assisted protocols for soluble polymer-supported syntheses have been described. Among the first examples of so-called liquid-phase synthesis were aqueous Suzuki couplings. Schotten and coworkers presented the use of polyethylene glycol (PEG)-bound aryl halides and sulfonates in these palladium-catalyzed cross-couplings [70]. The authors demonstrated that no additional phase-transfer catalyst (PTC) is needed when the PEG-bound electrophiles are coupled with appropriate aryl boronic acids. The polymer-bound substrates were coupled with 1.2 equivalents of the boronic acids in water under short-term microwave irradiation in sealed vessels in a domestic microwave oven (Scheme 7.62). Work-up involved precipitation of the polymer-bound biaryl from a suitable organic solvent with diethyl ether. Water and insoluble impurities need to be removed prior to precipitation in order to achieve high recoveries of the products. 

In a recent report by Wang, microwave-mediated Heck couplings were rapidly performed in water under phase-transfer conditions (Eq. 11.8) [22]. Villemin has also reported the use of water and acetonitrile in the context of using water-soluble ligands in microwave-assisted Heck couplings [23],... 

Hydrogenation is widely used for deproteetion of benzyl and benzyloxycarbonyl groups. Kappe s group [67,68] deprotected benzyl esters using continuous flow and then performed comparative experiments using conventional heating and microwave assisted transfer hydrogenation, whieh resulted in lower yields (53-65%) than when eompared to flow (80-85%). 

A series of polyphosphites, polyphosphates, polythiophosphates, and other polymers containing sulfone functions, based on 1, have also been described [17,119]. An efficient synthesis of polyethers from 1 and 1,8-dibromo or dimesyl octane by microwave-assisted phase transfer catalysis has been reported [120]. 

Bogdal, D. and Warzala, M., Microwave-assisted preparation of benzo[b]furans under solventless phase-transfer catalytic conditions, Tetrahedron, 2000, 56, 8769-8773. 

Similar reaction conditions as those by Bose were used for a range of other applications, for example, the synthesis of heterocycles. A combination of a microwave-assisted Paal-Knorr reaction15 with a transfer hydrogenation takes place in the preparation of 2,5-di- and 1,2,5-trisubstituted pyrroles from -l,4-diaryl-2-butene-l,4-diones in a one-pot operation. Hydrogenation was achieved with ammonium formates and 10% Pd/C as catalyst in PEG-200. Yields of up to 92% were obtained within 0.5-2 min (Scheme 4.2)16. 

Until now, hydrogen sources other than formates have been rarely reported in microwave-assisted transfer hydrogenations of carbon-carbon multiple bonds. An exception is a transfer hydrogenation of electron-deficient alkenes where a series of 1,4-dihydropyridines supported on silica gel were used as the hydrogen source (Scheme 4.6). The influences of electronic effects of the alkene, steric effects of the dihydropyridine and type and power of the microwave irradiation were studied24. 

Carbonyl)chlorohydridotris(triphenylphosphine)ruthenium(II) was used as a catalyst in the transfer hydrogenation of benzaldehyde with formic acid as a hydrogen source. Under these conditions, the reduction ofbenzaldehyde to benzyl alcohol is accompanied by esterification of the alcohol with the excess of formic acid to provide benzyl formate (Scheme 4.16). In this microwave-assisted reaction, the catalyst displayed improved turnover rates compared to the thermal reaction (280 vs. 6700 turnovers/h), thus leading to shorter reaction times36. 

Bose reported the dehalo genation of bromoanthracene, bromonaphthalene and several bromobenzenes under microwave-assisted hydrogen transfer conditions (ammonium formate, 10% Pd/C, ethylene glycol). An application of this reaction is the synthesis of several (3-lactams and isoquinoline derivatives14. 

The rapid microwave-assisted deprotection of N-benzyl carbamate (Cbz) and AT-benzyl (Bn) derivatives in solution as well as on solid support was reported by Daga et al.26 Within this report, amino groups protected as benzyl carbamates or with simple benzyl groups could be deprotected in a few minutes by microwave-assisted catalytic transfer hydrogenation with palladium charcoal in isopropanol, employing ammonium formate as the hydrogen donor (Scheme 7.6). Both MeO-PEG and PS Wang-resin were used as soluble and solid supports, respectively, in these reactions. 

Microwave-assisted Diels-Alder reactions of 9-substituted anthracenes with 2-acetamidoacrylate in DMF generate conformationally constrained bicyclic bisaryl a-amino acid derivatives with high regioselectivity.138 The Sc(OTf)3-catalysed Diels-Alder reaction of anthracenes with methyl vinyl ketone does not proceed via an electron-transfer process from anthracenes to the MVK-Sc(OTf)3 complex.139 (-)-(/ )-9-(l,2-Dimethoxyethyl)anthracene has been used as a chiral template in the Diels-Alder/retro-Diels-Alder sequence for the synthesis of a,j3-unsaturated lactams.140... 

A series of pyrrolidines was conveniently prepared in a microwave-assisted double alkylation of aniline derivatives with alkyl dihalides in water in the presence of K2CO3 as a base (Scheme 1) [12,13]. Although the reaction mixture could be regarded as a multi-phase system, as neither reactant was soluble in the mildly basic aqueous medium, the microwave-assisted reaction proceeded readily without the use of phase-transfer reagents. The amount of side-reactions such as hydrolysis of bromides to alcohols in an alkaline reaction medium was substantially suppressed compared to the conventional thermal conditions. The reaction conditions were sufficiently mild to tolerate a variety of functional groups in anilines such as hydroxyls, ketones and esters. Alkyl bromides and tosylates were equally efficient as alkylating agents. Notably, isolation and purification comprised simply of phase separations (filtration or decantation) of the desired product from the aqueous media. 

Scheme 3.11 Microwave-assisted transfer-hydrogenation of cinnamaldehyde with palladium on activated charcoal...

During microwave-assisted extraction (MAE), microwave energy is applied to heat a solvent or/and a sample in order to speed up transfer of the compound of interest from the sample to the solvent [43, 44]. Microwaves are an electromagnetic radiation with wavelengths ranging from as long as 1 m to as short as 1 mm, with frequencies between 1 and 100 GHz. 

---