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Ru-catalyzed isomerization of ω-alkenylboronates towards stereoselective synthesis of vinylboronates with subsequent in situ functionalization.

ABSTRACT: The stereoselective preparation of synthetically versatile vinylboronates from ω-alkenylboronates is achieved through a ruthenium-catalyzed isomerization reaction. A variety of di- and trisubstituted vinylboronates were conveniently produced and could be used as a new starting point for subsequent in situ remote functionalization through either a sequential Ru/Pd or Ru/Cu double catalytic system.

SUBMITTER: Ho GM

PROVIDER: S-EPMC8159340 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:The isomerization of estragole to trans-anethole is an important reaction and is industrially performed using an excess of NaOH or KOH in ethanol at high temperatures with very low selectivity. Simple Ru-based transition-metal complexes, under homogeneous, ionic liquid (IL)-supported (biphasic) and "solventless" conditions, can be used for this reaction. The selectivity of this reaction is more sensitive to the solvent/support used than the ligands associated with the metal catalyst. Thus, under the optimized reaction conditions, 100% conversion can be achieved in the estragole isomerization, using as little as 4 × 10-3 mol % (40 ppm) of [RuHCl(CO)(PPh3)3] in toluene, reflecting a total turnover number (TON) of 25 000 and turnover frequencies (TOFs) of up to 500 min-1 at 80 °C. Using a dimeric Ru precursor, [RuCl(μ-Cl)(η3:η3-C10H16)]2, in ethanol associated with P(OEt)3, a TON of 10 000 and a TOF of 125 min-1 are obtained with 100% conversion and 99% selectivity. These two Ru catalytic systems can be transposed to biphasic IL systems by using ionic-tagged P-ligands such as 1-(3-(diphenylphosphanyl)propyl)-2,3-dimethylimidazolium bis(trifluoromethanesulfonyl)imide immobilized in 1-(3-hydroxypropyl)-2,3-dimethylimidazolium bis(trifluoromethanesulfonyl) imide with up to 99% selectivity and almost complete estragole conversion. However, the reaction is much slower than that performed under solventless or homogeneous conditions. The use of ionic-tagged ligands significantly reduces the Ru leaching to the organic phase, compared to that in reactions performed under homogeneous conditions, where the catalytic system loses catalytic performance after the second recycling. Detailed kinetic investigations of the reaction catalyzed by [RuHCl(CO)(PPh3)3] indicate that a simplified kinetic model (a monomolecular reversible first-order reaction) is adequate for fitting the homogeneous reaction at 80 °C and under biphasic conditions. However, the kinetics of the reaction are better described if all of the elementary steps are taken into consideration, especially at 40 °C.

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Ru-catalyzed isomerization of ω-alkenylboronates towards stereoselective synthesis of vinylboronates with subsequent in situ functionalization.

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