Studies in organosilicon chemistry. 100. Pentacoordinate allylsiliconates in organic synthesis: synthesis of triethylammonium bis(catecholato)allylsiliconates and selective allylation of aldehydes

Abstract

The allyl(trimethoxy)silanes (I) react with catechol (II) in the presence of triethylamine (III) to form the siliconates (IV) mentioned in the title.

Indium(III) Chloride/Chlorotrimethylsilane as a Highly Active Lewis Acid Catalyst System for the Sakurai−Hosomi Reaction

“…The spectroscopic data of the products 3aϪi, [9b,16Ϫ19] 3fa, [9b] 3ga, [9b] 4b, [21] 5i, [21] and 6a [17] were in excellent agreement with reported compounds. …”

A Highly syn-Selective Allylation of Aldehydes in Water

“…1‐(4‐Cyanophenyl)‐2‐methyl‐3‐buten‐1‐ol (3o): 17 Prepared by the typical procedure from 1b (1 mmol) and p ‐cyanobenzaldehyde (1 mmol) in 94% yield (0.176 g, 0.94 mmol); syn : anti = 80:20. − IR (neat): $\tilde {\nu}$ = 3486, 2977, 2877, 2229, 1704, 1411, 910 cm −1 .…”

Beyond a solvent: triple roles of dimethylformamide in organic chemistry

“…As for the transition state, a six-membered molecule is suggested for the allylation of aldehydes (Scheme 89). [192][193][194] Among several solvents, DMF is the only solvent that was able to ensue this reaction. The 29 Si NMR spectra of 1Z showed that N,N-dimethylformamide coordinated to the Si atom of 1Z to yield the resulting ve or six coordinated organosilicate.…”