A One-Pot Synthesis of (E)-Disubstituted Alkenes by a Bimetallic [Rh-Pd]-Catalyzed Hydrosilylation/Hiyama Cross-Coupling Sequence

• Published in: Chemistry : a European journal Vol. 13; no. 32; pp. 8971 - 8978
• Main Authors: Thiot, Carine, Schmutz, Marc, Wagner, Alain, Mioskowski, Charles
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 01.01.2007; WILEY‐VCH Verlag; Wiley
• Subjects: Alkenes - chemical synthesis; Alkenes - chemistry; bimetallic catalyst; Catalysis; Chemistry; Chemistry, Multidisciplinary; cross-coupling; hydrosilylation; Molecular Structure; one-pot sequence; Organometallic Compounds - chemistry; Palladium - chemistry; Particle Size; Physical Sciences; Rhodium - chemistry; Science & Technology; selectivity modulation; Silanes - chemistry; Stereoisomerism; PALLADIUM; one-pot sequence; TERMINAL ALKYNES; STEREODIVERGENT SYNTHESES; (Z)-ALKENYLSILANES; DOMINO; bimetallic catalyst cross-coupling; MULTICOMPONENT REACTIONS; HETEROATOM SUBSTITUENTS; SONOGASHIRA; selectivity modulation; hydrosilylation; ALKENYLSILANES; TRANSFORMATIONS
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.200700811

A bimetallic [Rh–Pd] catalyst was prepared by soaking into an iodide ionic gel an equimolar solution of [RhCl(PPh3)3] and Pd(OAc)2 in CH2Cl2. 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(PPh3)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. Bimetallic catalysis: A practical one‐pot, highly stereoselective process for the synthesis of (E)‐disubstituted olefins by means of a sequential hydrosilylation/Hiyama coupling reaction, by using a bimetallic polyionic gel [Rh–Pd] catalyst is reported. This procedure allows rapid access to a variety of (E)‐disubstituted olefins in good overall yields (see scheme), without intermediate isolation. Due to an ionic‐gel‐mediated kinetic modulation, the bimetallic [Rh–Pd] system exhibits both higher chemo‐ and stereoselectivities than the combination of homogeneous catalysts.