Novel Dimerization, Alkoxylation, and Sulfidation of Olefins Catalyzed by RuCl3·nH2O

Abstract

Novel ruthenium-catalyzed reactions that employ ruthenium trichloride n-hydrate (RuCl3·nH2O) were investigated and dimerization, alkoxylation and sulfidation of olefins were noted. Adducts of Markovnikov type and anti-Markovnikov type were obtained in a stereospecific manner and in good yield, depending on the type of olefins used as the starting materials.

N -Heterocyclic carbene catalyzed tail-to-tail oligomerization of N , N -dimethylacrylamide (DMAA) and the search for the Stetter reaction of DMAA with benzaldehyde

“…In the presence of 1 mol % of carbene A and 1 mol % of benzoic acid as cocatalyst, benzoin (8), the Michael addition product of benzoin to DMAA (9), and the lactone (10) were formed. 12 The molecular structure of the Michael product 9 was unambiguously proven by X-ray crystallography ( Figure 1).…”

“…Sakakibara et al reported the Ru catalyzed dimerization of DMAA, along with the formation of a small amount of a non-characterized trimer. 9 In recent years, our group has studied intermediates of the NHC-catalyzed Umpolung of aldehydes. 10 Herein we report the tail-to-tail oligomerization of DMAA, the NHC-catalyzed cross coupling of DMAA with MMA, and the attempted Stetter reaction of benzaldehyde with DMAA.…”

In(OTf)3‐Catalyzed Highly Chemo‐ and Regioselective Head‐to‐Tail Heterodimerization of Vinylarenes with 1,1‐Diarylethenes

“…To the best of our knowledge, 1,1‐diarylethenes 8 (Scheme ) usually give indan products similar to 5 through cyclodimerization in the presence of Lewis acids, such as EtAlCl 2 ,9a RuCl 3 ⋅ n H 2 O,9b InBr 3 ,9c and BiCl 3 ,9d or aminium hexachloroantimonates 10. There is one example of aminium salt promoted heterodimerization of 1,1‐diphenylethene 8 a (Ar=Ph) with vinylferrocene, which occurs in 62 % yield, along with a 10 % yield of the head‐to‐tail dimer of vinylferrocene 10d.…”

A Mild Lewis‐Acid‐Catalyzed Method for Head‐to‐Tail Dimerization or Cyclization of tert‐Alcohols

“…The reaction proceeds with Markovnikov selectivity in both C−C bond forming steps. Several Lewis acids, including FeCl 3 , AlCl 3 , BiCl 3 , and RuCl 3 , and also Brønsted acids have been reported to catalyze this reaction . Unsaturated dimers are important chain‐transfer reagents in the production of polymers .…”