Synthesis of six-membered cyclic siloxanes via enyne metathesis with a ruthenium catalyst generated in situ |
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Authors: | David Smeril Myriam Clran Azucena Jimerez Perez Christian Bruneau Pierre H Dixneuf |
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Institution: | Institut de Chimie de Rennes, UMR 6509 Université de Rennes-CNRS, Organométalliques et Catalyse, Campus de Beaulieu, 35042, Rennes, France |
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Abstract: | The catalytic system in situ generated by combination of RuCl2(p-cymene)]2 as a ruthenium source, 1,3-bis(mesityl)imidazolinium chloride (MesH2ImCl) as a bulky electron-releasing carbene precursor and cesium carbonate as a base, is shown to be an efficient catalyst for the metathesis reaction of propargylic allylsilyl ethers R1---CCCR2---O---SiMe2---CH2CH=CH2. The metathesis products, the cyclic siloxanes, were obtained after complete conversion of the enynes in 67–87% isolated yields. These six-membered ring compounds contain the 1,3-diene unit that is used in Diels–Alder reaction and give access to heterobicyclic derivatives. The resulting cyclic siloxanes are selectively opened under oxidative conditions with H2O2 to afford allylic diols, with fluoride to form conjugated triene and under hydrogenation conditions with Pd/C catalyst to give a tetrasubstituted alkene. |
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Keywords: | Enyne metathesis Ruthenium catalyst Imidazolinium salt Cyclic siloxanes Allylsilanes |
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