Highly expedient synthesis of propargylic alcohols in the catalytic system
Bu4NOH/H2O/DMSO
I.A.Bidusenko, N.A.Cherimichkina, E.Yu.Schmidt, B.A.Trofimov
A.E. Favorsky Irkutsk institute of chemistry SB RAS, 1 Favorsky Str., 664033, Irkutsk, Russia
E-mail: boris_trofimov@irioch.irk.ru
Ethynylation of carbonyl compounds is one of the most important reactions of the carboncarbon bonds formation. The reaction affords propargylic alcohols, which represent multifacet
intermediates of fine and industrial organic synthesis. However, none of the existing methods for
the synthesis of propargylic alcohols is generally applicable to both aliphatic and aromatic carbonyl
compounds as well as to monosubstituted acetylenes, and, what is especially important, to acetylene
itself (industrially available feedstock).
We have developed a new and highly expedient synthesis of secondary and tertiary
propargylic alcohols of aliphatic, cycloaliphatic, aromatic and heteroaromatic series. The synthesis
is accomplished via organocatalytic ethynylation of aldehydes and ketones with acetylene (under
atmospheric pressure) and its monosubstituted derivatives (including functionalized acetylenes)
using catalytic composition Bu4NOH/H2O/DMSO.[1]
The synthesis opens a facile and environmentally benign (metal-free) way to a plethora of
propargylic alcohols, thus essentially expanding the scope of their application as valuable building
blocks for the preparation of fragrance compounds, vitamins, pheromones, ecologically friendly
insecticides as well as steel acidic corrosion inhibitors and nonionic surfactants.
This
work
was
supported
Foundation (Project №. 14-13-00588).
by
a
grant
of
Russian
Scientific
References
[1] E. Yu. Schmidt, N. A. Cherimichkina, I. A. Bidusenko, N. I. Protzuk, B. A. Trofimov Eur. J. Org. Chem. 2014,
4663–4670