Ionic Ga-Complexes of Alkylidene- and Arylmethylidenemalonates and Their Reactions with Acetylenes: An In-Depth Look into the Mechanism of the Occurring Gallium Chemistry

Ionic Ga-Complexes of Alkylidene- and Arylmethylidenemalonates and Their Reactions with Acetylenes: An In-Depth Look into the Mechanism of the Occurring Gallium Chemistry Full article

Journal

Journal of the American Chemical Society
ISSN: 0002-7863 , E-ISSN: 1520-5126

Output data

Year: 2018, Volume: 140, Number: 43, Pages: 14381-14390 Pages count : 10 DOI: 10.1021/jacs.8b08913

Authors

Novikov Roman A. ^1,2 , Denisov Dmitry A. ¹ , Potapov Konstantin V. ¹ , Tkachev Yaroslav V. ² , Shulishov Evgeny V. ¹ , Tomilov Yury V. ¹

Affiliations

1	N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky Prospekt, 119991 Moscow, Russian Federation
2	Engelhardt Institute of Molecular Biology, Russian Academy of Sciences, 32 Vavilov Street, 119991 Moscow, Russian Federation

A new synthetic concept was suggested in the chemistry of substituted methylidenemalonates that enables their utilization as 1,2-zwitterionic synthons. This strategy is to generate liquid ionic Ga complexes from methylidenemalonates and GaHal3 with a strict 3/4 composition and then use them in further synthesis. A number of complexes with different metal halides have been synthesized and studied in detail. The unique properties of gallium among all metals have been demonstrated and explained. On the basis of the discovered new class of gallium complexes of methylidenemalonates, a number of novel reactions with acetylenes have been elaborated, which are unknown in the conventional chemistry of methylidenemalonates. The main demonstrated process is a three-component addition to a triple bond involving halide anions, leading to the formation of polyfunctional vinyl halides with high E-selectivity. The mechanism has been studied experimentally in fine detail. Application of specially optimized 71Ga NMR spectroscopy makes it possible to take an in-depth look into the gallium chemistry in a new light. In particular, the key participation of GaHal4– anions in the occurring transformations has been established.

Novikov R.A. , Denisov D.A. , Potapov K.V. , Tkachev Y.V. , Shulishov E.V. , Tomilov Y.V.
Ionic Ga-Complexes of Alkylidene- and Arylmethylidenemalonates and Their Reactions with Acetylenes: An In-Depth Look into the Mechanism of the Occurring Gallium Chemistry
Journal of the American Chemical Society. 2018. V.140. N43. P.14381-14390. DOI: 10.1021/jacs.8b08913 WOS Scopus OpenAlex

≡ Web of science:	WOS:000449239700049
≡ Scopus:	2-s2.0-85055091754
≡ OpenAlex:	W2894689893