Electroreductive hydrocoupling of activated olefins with ketones or aldehydes in the presence of trimethylchlorosilane

Contributions of organic electrosynthesis to green chemistry

“…Crossed cathodic coupling between aldehydes, ketones and a,b-unsaturated carbonyl compounds is possible in aqueous or aprotic solvents to form g-lactones (Scheme 29) [54,57]. The intramolecular cathodic cross coupling between a carbonyl group and a double bond produces cyclopentanes in high diastereoselectivity; in this cyclization possibly radicals or anion radicals are involved (Scheme 30) [58].…”

Electrochemical Synthesis of Functional Organosilanes II: Direct Electrochemical Formation of Si-C Bonds

“…However, it is known from literature that the aggregation and dissociation behavior of LiCl in THF can be described as in eq. 1 and 2: 19 (LiCl) 2 Li…”

“…Examples include the fundamental industrial Direct Process, Grignard-type processes, Wurtz-Fittig coupling reactions and transition metal-catalyzed reactions. 1 One practical method that can be utilized on the laboratory scale is the electrochemical formation of Si-C bonds, which basically involves the reduction of the organic substrate followed by an attack of the electrogenerated C-nucleophile on the Si-Cl bond of a chlorosilane (Scheme 1).In the early 1980s, Shono et al 2,3 and Yoshida et al 4 showed that this kind of electroreductive cross-coupling is possible in a divided cell with Pt anodes, but no defined anodic oxidation products were reported. In the great majority of the following papers reporting electrochemical Si-C bond formation, Me 3 SiCl was used as the silyl source.…”

“…In the early 1980s, Shono et al 2,3 and Yoshida et al 4 showed that this kind of electroreductive cross-coupling is possible in a divided cell with Pt anodes, but no defined anodic oxidation products were reported. In the great majority of the following papers reporting electrochemical Si-C bond formation, Me 3 SiCl was used as the silyl source.…”

“…(p-Methoxyphenyl)dimethylsilane(2).-(a) 3.32 g (35 mmol) of chlorodimethylsilane and 5.0 g (35 mmol) of 4-chloroanisole were electrolyzed at 15 mA for 169 hours (2.7 F). After standard work up, 4.4 g of the crude product were isolated.…”