Synthesis of Ethers from Carbonyl Compounds by Reductive Etherification Catalyzed by Iron(III) and Silyl Chloride

Abstract

A simple iron-and silyl chloride catalyzed method for the preparation of symmetrical and nonsymmetrical ethers is presented. Various aldehydes and ketones were reductively etherified by using triethylsilane as a reducing agent in the presence of 2 mol% of iron(III) oxo acetate and 8 mol% of chloro(trimethyl)silane. The reactions can be carried out at ambient temperatures and pressures with ethyl acetate as the solvent.

Direct Cross-Coupling of Alcohols with O-Nucleophiles Mediated by N-Iodosuccinimide as a Precatalyst under Mild Reaction Conditions

“…1 H NMR and 13 C NMR spectra for (methoxymethylene)dibenzene (4), Figure S5: 1 H NMR and 13 C NMR spectra for (±) 4,4 -(oxybis(phenylmethylene))bis(methylbenzene) (6), Figure S6: 1 H NMR and 13 C NMR spectra for (±) 1-(methoxy(phenyl)methyl)-4-methylbenzene (7), Figure S7: 1 H NMR and 13 C NMR spectra for 1-chloro-4-(methoxy(phenyl)methyl)benzene (9), Figure S8: 1 H NMR and 13 C NMR spectra for (ethoxymethylene)dibenzene (11), Figure S9: 1 H NMR and 13 C NMR spectra for isopropoxydiphenylmethane (13), Figure S10: 1 H NMR and 13 C NMR spectra for 4,4'-(oxybis(methylene))bis(methylbenzene) (23), Figure S11: 1 H NMR and 13 C NMR spectra for ((benzyloxy)methylene)dibenzene (29), Figure S12: 1 H NMR and 13 C NMR spectra for (((4-methylbenzyl)oxy)methylene)dibenzene (30), Figure S13: 1 H NMR and 13 C NMR spectra for (((4-chlorobenzyl)oxy)methylene)dibenzene (31), Figure S14: Thermal Gravimetric (TG) analysis of the NIS. References [24][25][26][27][28][29][30][31][32][33] are cited in the Supplementary Materials.…”

Breaking C–O Bonds with Uranium: Uranyl Complexes as Selective Catalysts in the Hydrosilylation of Aldehydes

“…Such reductive etherification of aldehyde has been reported with various Lewis acids, such as Me 3 SiX (X = I, OTf), Fe­(III), M­(OTf) 3 (M = In, Sc, Bi, Ga, Al), M­(OTf) 2 (M = Cu, Zn) as well as several Sb­(III) and Sb­(V) compounds . Several reports describe the reductive coupling of aldehydes and ketones to ethers with organosilicon reagents in the presence of Lewis acid activators.…”

“…The reduction of benzaldehyde (2) with a uranyl catalyst and a hydrosilane was initially investigated as a model reaction Such reductive etherification of aldehyde has been reported with various Lewis acids, such as Me 3 SiX (X = I, 19 OTf), Fe(III), 20 M(OTf) 3 (M = In, 21 = Cu, 23 Zn 24 ) as well as several Sb(III) 25 and Sb(V) 26 compounds. 27 Several reports describe the reductive coupling of aldehydes and ketones to ethers with organosilicon reagents in the presence of Lewis acid activators.…”

Poly(silyl ether)s (silyl ether copolymers) via hydrosilylation of carbonyl compounds

“…In the RER protocol, carbonyl compounds in the presence of silane and a Brønsted or Lewis acid catalyst afford the synthesis of symmetric and unsymmetrical ethers. 8–28 However, the silyl ether is produced rather than the corresponding ether in the hydrosilylation. Notably, both mechanisms seem to cover the competing reaction pathways.…”