A catalyst-free synthesis of asymmetric diaryl ketones from aryltins

A series of diaryl ketones have been synthesized in good yields (40-78%) through the catalyst-free reaction of trimethylarylstannanes with aroyl chlorides in chlorobenzene as solvent. In addition, an attractive feature is that these reactions are completely regioselective making possible the synthesis of diarylketones which are not usually available under the influence of the directing forces of the substituents present in the aromatic ring. Also, the reaction conditions are mild enough to be applied to acid sensitive molecules.     

Selective synthesis of mono- and distannylpyridines from chloropyridinols via an SRN1 mechanism

A selective two-step synthesis of either mono- or distannylated pyridines from commercially available pyridinols, involving its conversion to the corresponding diethyl pyridyl phosphates (pyDEP) followed by the reaction with Me₃SnNa in liquid ammonia, is described.The results obtained clearly indicate that the reactions proceed through an unimolecular radical nucleophilic substitution mechanism (S_RN1) with intermediacy of a monosubstitution product.     

Strategies for the synthesis of bi- and triarylic materials starting from commercially available phenols

A series of arylstannanes have been synthesized, through an S_RN1 mechanism, in good to excellent yields (74%-99%) by the photostimulated reaction of trimethyl stannyl ion with substrates supporting different nucleofugal groups. The arylstannanes thus obtained were suitable intermediates for Stille cross-coupling reactions leading to asymmetric bi- and triaryl compounds in acceptable global yields. An attractive feature of this route is that simple commercially available benzenediols, chloro- and methoxy phenols might be useful starting substrates, leading the latter to higher global yields of products in fewer steps. The strategies proposed open a broad synthetic tool.     

Efficient catalyst-free bi- and triaroylation of aromatic rings in a single step

The exceptional leaving group ability of the trimethylstannyl group in electrophilic aromatic substitutions makes possible the synthesis, in a single step, of bi- and triaroylarenes through the catalyst-free, regioselective reaction of bi- and tristannylarenes with different aroyl halides in o-dichlorobenzene as solvent. Specific di- and triketones are obtained in good to excellent yields (45-83%).     

Three‐step synthesis of arylpolyboronic acids from phenols via organotin compounds

In this paper we describe a three‐step synthesis of aryldi‐ and triboronic acids starting from phenols. Several substituted phenols (I) were converted into the corresponding aryldiethylphosphates (II) in good to excellent yields. The latter, on reaction with sodium trimethylstannide in liquid ammonia, under irradiation, afforded the aryl‐ and heteroarylpoly(trimethylstannyl) derivatives in 65–90% yield. The third step is the reaction of the organotin compounds with borane in THF, which leads to the corresponding arylpolyboronic acids in around 80% yield. In order to confirm their structure, some of the diboronic acids were converted into the corresponding pinacol esters. The results obtained in a study on the synthesis of various terphenyls through double and triple Suzuki couplings catalyzed by palladium acetate between the obtained arylpolyboronic acids and various aryl halides are also reported. These reactions proceeded with an average 65% yield, and also enabled us to confirm the structures of some of the diboronic acids. The structure of the new compounds was determined by ¹H, ¹³C and ¹¹⁹Sn NMR spectroscopy, mass spectrometry and IR spectroscopy. Copyright © 2007 John Wiley & Sons, Ltd.     

Selective synthetic routes to sterically hindered unsymmetrical diaryl ketones via arylstannanes

Bulky arylstannanes and bulky aroyl chlorides are good reaction partners for the synthesis of two-, three-, and even four-ortho-substituted benzophenones, in good to excellent isolated yields (47-91%). Three simple and direct routes, with differential advantages, are proposed: (i) a catalyst-free protocol, in o-dichlorobenzene (ODCB) at 180 °C; (ii) a room temperature protocol, using AlCl(3) (0.5 equiv), in dichloromethane (DCM); and (iii) a solvent-free, indium-promoted procedure. A radical mechanism is proposed for the indium-mediated reactions.