A one-pot synthesis of (E)-disubstituted alkenes by a bimetallic [Rh-Pd]-catalyzed hydrosilylation/hiyama cross-coupling sequence.
A bimetallic [Rh-Pd] catalyst was prepared by soaking into an iodide ionic gel an equimolar solution of [RhCl(PPh(3))(3)] and Pd(OAc)(2) in CH(2)Cl(2). Its catalytic activity was evaluated by rhodium-catalyzed hydrosilylation (H), palladium-catalyzed Hiyama coupling (C), and in the one-pot hydrosilylation/Hiyama coupling sequence (H/C). It was found that the homogeneous combination [RhCl(PPh(3))(3)]/NaI was a superior system compared to the polyionic mono- and bimetallic rhodium catalysts in the hydrosilylation of terminal alkynes. Interestingly, the most effective catalyst in terms of stereo- and chemoselectivities was observed to be the bimetallic ionic gel [Rh-Pd] in the one-pot process leading to (E)-alkenes with good yields. The remarkable stereocontrol is ascribed to a beneficial Pd-catalyzed isomerization from the mixture of stereoisomeric vinylsilanes obtained in the initial hydrosilylation step into the more stable (E)-adduct. The [Rh-Pd] heterogeneous catalyst also showed a higher chemoselectivity than the homogeneous catalytic combination, and no detrimental formation of Sonogashira side product was observed due to an ionic-gel-mediated kinetic modulation. To illustrate its scope and limitations, the described one-pot bimetallic catalytic sequence was extended to functionalized terminal alkynes and various iodide substrates. Conjugated systems, such as hydroxycinnamaldehyde, dienes, and trienes, were synthesized in good overall yields. To avoid deactivation of the Rh species, N-heterocyclic iodides had to be added sequentially after completion of hydrosilylation.
Laboratoire de Synthèse Bio-Organique, Université Louis Pasteur, Faculté de Pharmacie, 74 route du Rhin, 67401 Illkirch-Graffenstaden, France.
Carine
C
Thiot
Marc
M
Schmutz
Alain
A
Wagner
Charles
C
Mioskowski
D000475:Alkenes / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D010165:Palladium / Q000737:chemistry*; D010316:Particle Size; D012238:Rhodium / Q000737:chemistry*; D012821:Silanes / Q000737:chemistry*; D013237:Stereoisomerism
D000475:Alkenes; D009942:Organometallic Compounds; D012821:Silanes; D010165:Palladium; D012238:Rhodium