Computed CH Acidity of Biaryl Compounds and Their Deprotonative Metalation by Using a Mixed Lithium/Zinc‐TMP Base
Identifieur interne : 000F00 ( Main/Exploration ); précédent : 000E99; suivant : 000F01Computed CH Acidity of Biaryl Compounds and Their Deprotonative Metalation by Using a Mixed Lithium/Zinc‐TMP Base
Auteurs : Jean-Paul Kadiyala ; Jean-Paul Tilly ; Elisabeth Nagaradja ; Elisabeth Roisnel [France] ; Elisabeth Matulis [Biélorussie] ; Elisabeth Ivashkevich [Biélorussie] ; Elisabeth Halauko ; Elisabeth Chevallier ; Elisabeth Gros [France] ; Elisabeth MonginSource :
- Chemistry – A European Journal [ 0947-6539 ] ; 2013-06-10.
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Abstract
With the aim of synthesizing biaryl compounds, several aromatic iodides were prepared by the deprotonative metalation of methoxybenzenes, 3‐substituted naphthalenes, isoquinoline, and methoxypyridines by using a mixed lithium/zinc‐TMP (TMP=2,2,6,6‐tetramethylpiperidino) base and subsequent iodolysis. The halides thus obtained, as well as commercial compounds, were cross‐coupled under palladium catalysis (e.g., Suzuki coupling with 2,4‐dimethoxy‐5‐pyrimidylboronic acid) to afford various representative biaryl compounds. Deprotometalation of the latter compounds was performed by using the lithium/zinc‐TMP base and evaluated by subsequent iodolysis. The outcome of these reactions has been discussed in light of the CH acidities of these substrates, as determined in THF solution by using the DFT B3LYP method. Except for in the presence of decidedly lower pKa values, the regioselectivities of the deprotometalation reactions tend to be governed by nearby coordinating atoms rather than by site acidities. In particular, azine and diazine nitrogen atoms have been shown to be efficient in inducing the reactions with the lithium/zinc‐TMP base at adjacent sites (e.g., by using 1‐(2‐methoxyphenyl)isoquinoline, 4‐(2,5‐dimethoxyphenyl)‐3‐methoxypyridine, or 5‐(2,5‐dimethoxyphenyl)‐2,4‐dimethoxypyrimidine as the substrate), a behavior that has already been observed upon treatment with lithium amides under kinetic conditions. Finally, the iodinated biaryl derivatives were involved in palladium‐catalyzed reactions.
Url:
DOI: 10.1002/chem.201300552
Affiliations:
- Biélorussie, France
- Grand Est, Lorraine (région), Région Bretagne
- Metz, Nancy, Rennes
- Université de Lorraine, Université de Rennes 1
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The halides thus obtained, as well as commercial compounds, were cross‐coupled under palladium catalysis (e.g., Suzuki coupling with 2,4‐dimethoxy‐5‐pyrimidylboronic acid) to afford various representative biaryl compounds. Deprotometalation of the latter compounds was performed by using the lithium/zinc‐TMP base and evaluated by subsequent iodolysis. The outcome of these reactions has been discussed in light of the CH acidities of these substrates, as determined in THF solution by using the DFT B3LYP method. Except for in the presence of decidedly lower pKa values, the regioselectivities of the deprotometalation reactions tend to be governed by nearby coordinating atoms rather than by site acidities. In particular, azine and diazine nitrogen atoms have been shown to be efficient in inducing the reactions with the lithium/zinc‐TMP base at adjacent sites (e.g., by using 1‐(2‐methoxyphenyl)isoquinoline, 4‐(2,5‐dimethoxyphenyl)‐3‐methoxypyridine, or 5‐(2,5‐dimethoxyphenyl)‐2,4‐dimethoxypyrimidine as the substrate), a behavior that has already been observed upon treatment with lithium amides under kinetic conditions. Finally, the iodinated biaryl derivatives were involved in palladium‐catalyzed reactions.</div></front></TEI><affiliations><list><country><li>Biélorussie</li><li>France</li></country><region><li>Grand Est</li><li>Lorraine (région)</li><li>Région Bretagne</li></region><settlement><li>Metz</li><li>Nancy</li><li>Rennes</li></settlement><orgName><li>Université de Lorraine</li><li>Université de Rennes 1</li></orgName></list><tree><noCountry><name sortKey="Chevallier, Elisabeth" sort="Chevallier, Elisabeth" uniqKey="Chevallier E" first="Elisabeth" last="Chevallier">Elisabeth Chevallier</name><name sortKey="Halauko, Elisabeth" sort="Halauko, Elisabeth" uniqKey="Halauko E" first="Elisabeth" last="Halauko">Elisabeth Halauko</name><name sortKey="Kadiyala, Jean Aul" sort="Kadiyala, Jean Aul" uniqKey="Kadiyala J" first="Jean-Paul" last="Kadiyala">Jean-Paul Kadiyala</name><name sortKey="Mongin, Elisabeth" sort="Mongin, Elisabeth" uniqKey="Mongin E" first="Elisabeth" last="Mongin">Elisabeth Mongin</name><name sortKey="Nagaradja, Elisabeth" sort="Nagaradja, Elisabeth" uniqKey="Nagaradja E" first="Elisabeth" last="Nagaradja">Elisabeth Nagaradja</name><name sortKey="Tilly, Jean Aul" sort="Tilly, Jean Aul" uniqKey="Tilly J" first="Jean-Paul" last="Tilly">Jean-Paul Tilly</name></noCountry><country name="France"><region name="Région Bretagne"><name sortKey="Roisnel, Elisabeth" sort="Roisnel, Elisabeth" uniqKey="Roisnel E" first="Elisabeth" last="Roisnel">Elisabeth Roisnel</name></region><name sortKey="Gros, Elisabeth" sort="Gros, Elisabeth" uniqKey="Gros E" first="Elisabeth" last="Gros">Elisabeth Gros</name></country><country name="Biélorussie"><noRegion><name sortKey="Matulis, Elisabeth" sort="Matulis, Elisabeth" uniqKey="Matulis E" first="Elisabeth" last="Matulis">Elisabeth Matulis</name></noRegion><name sortKey="Ivashkevich, Elisabeth" sort="Ivashkevich, Elisabeth" uniqKey="Ivashkevich E" first="Elisabeth" last="Ivashkevich">Elisabeth Ivashkevich</name></country></tree></affiliations></record>Pour manipuler ce document sous Unix (Dilib)
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