Piotr Pawluć

New One-Pot Synthesis of (E)-β-Aryl Vinyl Halides from Styrenes

A new, efficient protocol for the highly stereoselective one-pot synthesis of (E)-beta-aryl vinyl iodides and (E)-beta-aryl vinyl bromides from styrenes based on sequential ruthenium-catalyzed silylative coupling-N-halosuccinimide-mediated halodesilylation reactions is reported.

(E)-9-(2-iodovinyl)-9H-carbazole: a new coupling reagent for the synthesis of π-conjugated carbazoles.

The one-pot synthesis of (E)-9-(2-iodovinyl)-9H-carbazole via sequential ruthenium-catalyzed silylative coupling of N-vinylcarbazole with vinyltrimethylsilane and iododesilylation is reported. Its use as a new building block in the palladium-catalyzed Sonogashira and Suzuki-Miyaura coupling reactions to yield new carbazole-containing (E)-but-1-en-3-ynes and (E,E)-buta-1,3-dienes is demonstrated.

Highly stereo- and regioselective synthesis of a phenylene-silylene-vinylene polymer via ruthenium-catalyzed polycondensation

[RuCl2(CO)3]2 catalyzed cross-coupling polycondensation of 1,4-bis(vinyldimethylsilyl)benzene (A) appears to be a new, very efficient, method for highly stereo- and regioselective synthesis of phenylene‐ silylene‐vinylene polymers (B).

A new selective approach to unsymmetrical siloxanes and germasiloxanes via O-metalation of silanols with 2-methylallylsilanes and 2-methylallylgermanes

A scandium(III) trifluoromethanesulfonate-catalyzed O-metalation of silanols with 2-methylallylsilanes and 2-methylallylgermanes leading to siloxane or germasiloxane bond formation under mild conditions with evolution of isobutylene is described.

One-pot synthesis of (E)-styryl ketones from styrenes.

A new, efficient protocol for the highly stereoselective one-pot synthesis of (E)-styryl ketones from styrenes based on sequential ruthenium-catalyzed silylative coupling-rhodium-catalyzed desilylative acylation reactions is reported.

Ruthenium-catalysed hydrosilylation of carbon–carbon multiple bonds

Ruthenium-based complexes are generally considered to be efficient catalysts due to their high activity and electron transfer features. Although there are a limited number of highly selective olefin hydrosilylation protocols with ruthenium catalysts, recently a wide variety of the ruthenium complexes has been reported as unique catalyst precursors for the regiocontrolled hydrosilylation of alkynes. The ruthenium-catalysed hydrosilylation of alkynes represents one of the most efficient and straightforward methods for the synthesis of stereodefined vinylsilanes, which are particularly attractive scaffolds for further transformations including palladium-catalysed cross-coupling with organic halides or desilylative oxidation. The article highlights recent developments and covers the literature from the last two decades with respect to the ruthenium-catalysed hydrosilylation of alkenes and alkynes with particular emphasis on its application in organic synthesis.

Synthesis of Phenylene-Silylene-Vinylene Polymer and Copolymer by Ruthenium-Catalyzed Silylative Cross-Coupling Reaction

RuH(OAc)(CO)(PPh 3 ) 2 catalyzed silylative croos-coupling polycondensation of 4-(dimethylvinylsilyl)styrene (2) and copolycondensation of 1,4-divinylbenzene (4) with 1,4-bis(dimethylvinylsilyl)benzene (5) appeared to be a novel synthetic route for highly stereo- and regioselective synthesis of phenylene(arylene)-silylene-vinylene polymers.

Ruthenium-catalyzed silylation of 1,3-butadienes with vinylsilanes.

A novel method for the synthesis of 1-silyl-substituted 1,3-butadienes, based on [RuHCl(CO)(PCy3)2]-catalyzed silylative coupling of terminal (E)-1,3-dienes with vinylsilanes, is reported. The reaction provides a facile and straightforward access to (E,E)-dienylsilanes in a highly stereoselective fashion (especially for aryl-substituted dienes) and opens a valuable and general synthetic route for the direct catalytic silylation of conjugated dienes with elimination of ethylene as a single byproduct. Preliminary results on synthetic application of the synthesized silylated 1,3-butadienes in desilylation reactions are described.

Highly Selective Hydrothiolation of Unsaturated Organosilicon Compounds Catalyzed by Scandium(III) Triflate

The first use of a Lewis acid catalyst in the addition reaction of both aromatic and aliphatic thiols to unsaturated organosilicon compounds is reported. In catalytic tests, scandium(III) triflate demonstrates high catalytic activity in this process. Under mild conditions (25u2009°C, room temperature, 1-10u2005h) a number of thioether-functionalized organosilicon species are obtained with appreciable selectivity. This study constitutes the first example of allylsilane hydrothiolation that gives the Markovnikov regioisomer as the main product. Ethynylsilanes are also successfully used in the hydrothiolation reaction in the presence of Sc(OTf)3 .

Silylative coupling of olefins with vinylsilanes in the synthesis of functionalized alkenes

The development of highly selective methods for the synthesis of functionalized olefins, based on sequential catalytic reactions of organometallic reagents, has been the subject of extensive study because of their versatile applications in organic synthesis and materials science. The silylative coupling of olefins with vinyl-substituted organosilicon compounds (discovered in our group) represents one of the most efficient and straightforward methods for the synthesis of stereodefined alkenylsilanes and bis(silyl)alkenes, which are particularly attractive scaffolds for further transformations including palladium-catalyzed cross-coupling with organic halides (Hiyama coupling) or electrophile-induced desilylation. The article highlights the recent developments and covers the literature mainly from the last decade in the sequential (also one-pot) synthetic strategies including ruthenium-catalyzed silylative coupling followed by desilylative cross-coupling, acylation and halogenation, leading to stereodefined organic derivatives such as (E)-alkenyl halides, (E)-α,β-unsaturated ketones or arylene-(E)-vinylene derivatives which are widely applied as fine chemicals, functional materials or building blocks in organic synthesis.