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On the Directing Effect of Boronate Groups in the Lithiation of Boronated Thiophenes

Identifieur interne : 000320 ( Istex/Curation ); précédent : 000319; suivant : 000321

On the Directing Effect of Boronate Groups in the Lithiation of Boronated Thiophenes

Auteurs : Elena Borowska ; Krzysztof Durka ; Sergiusz Luli Ski [Pologne] ; Janusz Serwatowski ; Krzysztof Wo Niak [Pologne]

Source :

European Journal of Organic Chemistry [ 1434-193X ] ; 2012-04.

RBID : ISTEX:126573043BECD863BF136C98834FD93ADF8D8495

English descriptors

KwdEn :
- Acidity, Azaesters, Borocanyl, Borocanyl group, Boronate, Boronated, Boronated thiophenes, Boronates, Boronation, Calcd, Cdcl3, Chem, Computational, Computational studies, Crude product, Deprotonation, Deprotonation energies, Derivative, Diboronic acid, Diethyl, Diethyl ether, Durka, Ester, Et2o, Ether, Full paper, Functional group, Furan, Gmbh, Hydrogen atoms, Internal temperature, Intramolecular coordination, Kgaa, Lithiated, Lithiation, Lithiation energies, Lithium, Lithium atom, Lithium dialkylamides, Ltmp, Lulinski, Metalation, Mmol, Nbuli, Organic phase, Proton, Proton abstraction, Reaction pathways, Regioselective formation, Room temperature, Solid residue, Thiophene, Thiopheneboronic, Thiophenes, Transition states, Verlag, Verlag gmbh, Water phase, Weinheim, White powder.
Teeft :
- Acidity, Azaesters, Borocanyl, Borocanyl group, Boronate, Boronated, Boronated thiophenes, Boronates, Boronation, Calcd, Cdcl3, Chem, Computational, Computational studies, Crude product, Deprotonation, Deprotonation energies, Derivative, Diboronic acid, Diethyl, Diethyl ether, Durka, Ester, Et2o, Ether, Full paper, Functional group, Furan, Gmbh, Hydrogen atoms, Internal temperature, Intramolecular coordination, Kgaa, Lithiated, Lithiation, Lithiation energies, Lithium, Lithium atom, Lithium dialkylamides, Ltmp, Lulinski, Metalation, Mmol, Nbuli, Organic phase, Proton, Proton abstraction, Reaction pathways, Regioselective formation, Room temperature, Solid residue, Thiophene, Thiopheneboronic, Thiophenes, Transition states, Verlag, Verlag gmbh, Water phase, Weinheim, White powder.

Abstract

An investigation of thiophene boronates has revealed the usefulness of a metalation reaction in the synthesis of various lithiated thiophene boronates, which were further converted to functionalized thiopheneboronic derivatives. The lithiation of 2‐ and 3‐thienylboronic N‐butyldiethanolamine (BDEA) esters with lithium diisopropylamide and lithium 2,2,6,6‐tetramethylpiperidide showed that both boronated thiophenes were readily deprotonated. In the latter case, lithiation at the 2‐position adjacent both to sulfur and the borocanyl group is thermodynamically favoured due to the significant stabilizing effect of the borocanyl group. Further derivatization with a range of electrophiles followed by hydrolysis afforded various 2‐substituted 3‐thiopheneboronic acids. Lithiation of the corresponding thiopheneboronic “ate” complexes of the type [ThB(OR)3]Li revealed that the 2‐thienyl derivatives could not be effectively deprotonated, whereas the “ate” complex, [3‐ThB(OEt)3]Li, was selectively lithiated with nBuLi at C‐2. This points to a directing effect of the anionic boronate moiety. The resulting bimetallic species, [(2‐Li‐3‐Th)B(OEt)3]Li, underwent ring‐closing dimerization upon heating to give, after subsequent hydrolysis, 4,8‐dihydro‐4,8‐dihydroxy‐p‐diborino[2,3‐b:5,6‐b′]dithiophene ― a cyclic diborinic acid. A computational study of the lithiation of boronated thiophenes and furans proved that boronation decreases ring‐proton acidity. This effect is much stronger for the boronic “ate” complexes than for the corresponding neutral BDEA esters. Calculations of the transition states have shown that the specific directing effect of boronate groups in 3‐thienyl derivatives is due to intramolecular oxygen–lithium coordination.

Url:

https://api.istex.fr/document/126573043BECD863BF136C98834FD93ADF8D8495/fulltext/pdf

DOI: 10.1002/ejoc.201101764

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Elena Borowska

<affiliation><mods:affiliation>Warsaw University of Technology, Faculty of Chemistry, Department of Physical Chemistry, Noakowskiego 3, 00‐664 Warsaw, Poland, Fax: +4822‐6282741</mods:affiliation>
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Krzysztof Durka

<affiliation><mods:affiliation>E-mail: kdurka@gmail.com</mods:affiliation>
<wicri:noCountry code="no comma">E-mail: kdurka@gmail.com</wicri:noCountry>
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Janusz Serwatowski

<affiliation><mods:affiliation>Warsaw University of Technology, Faculty of Chemistry, Department of Physical Chemistry, Noakowskiego 3, 00‐664 Warsaw, Poland, Fax: +4822‐6282741</mods:affiliation>
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Le document en format XML

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<term>Azaesters</term>
<term>Borocanyl</term>
<term>Borocanyl group</term>
<term>Boronate</term>
<term>Boronated</term>
<term>Boronated thiophenes</term>
<term>Boronates</term>
<term>Boronation</term>
<term>Calcd</term>
<term>Cdcl3</term>
<term>Chem</term>
<term>Computational</term>
<term>Computational studies</term>
<term>Crude product</term>
<term>Deprotonation</term>
<term>Deprotonation energies</term>
<term>Derivative</term>
<term>Diboronic acid</term>
<term>Diethyl</term>
<term>Diethyl ether</term>
<term>Durka</term>
<term>Ester</term>
<term>Et2o</term>
<term>Ether</term>
<term>Full paper</term>
<term>Functional group</term>
<term>Furan</term>
<term>Gmbh</term>
<term>Hydrogen atoms</term>
<term>Internal temperature</term>
<term>Intramolecular coordination</term>
<term>Kgaa</term>
<term>Lithiated</term>
<term>Lithiation</term>
<term>Lithiation energies</term>
<term>Lithium</term>
<term>Lithium atom</term>
<term>Lithium dialkylamides</term>
<term>Ltmp</term>
<term>Lulinski</term>
<term>Metalation</term>
<term>Mmol</term>
<term>Nbuli</term>
<term>Organic phase</term>
<term>Proton</term>
<term>Proton abstraction</term>
<term>Reaction pathways</term>
<term>Regioselective formation</term>
<term>Room temperature</term>
<term>Solid residue</term>
<term>Thiophene</term>
<term>Thiopheneboronic</term>
<term>Thiophenes</term>
<term>Transition states</term>
<term>Verlag</term>
<term>Verlag gmbh</term>
<term>Water phase</term>
<term>Weinheim</term>
<term>White powder</term>
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<term>Azaesters</term>
<term>Borocanyl</term>
<term>Borocanyl group</term>
<term>Boronate</term>
<term>Boronated</term>
<term>Boronated thiophenes</term>
<term>Boronates</term>
<term>Boronation</term>
<term>Calcd</term>
<term>Cdcl3</term>
<term>Chem</term>
<term>Computational</term>
<term>Computational studies</term>
<term>Crude product</term>
<term>Deprotonation</term>
<term>Deprotonation energies</term>
<term>Derivative</term>
<term>Diboronic acid</term>
<term>Diethyl</term>
<term>Diethyl ether</term>
<term>Durka</term>
<term>Ester</term>
<term>Et2o</term>
<term>Ether</term>
<term>Full paper</term>
<term>Functional group</term>
<term>Furan</term>
<term>Gmbh</term>
<term>Hydrogen atoms</term>
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<term>Intramolecular coordination</term>
<term>Kgaa</term>
<term>Lithiated</term>
<term>Lithiation</term>
<term>Lithiation energies</term>
<term>Lithium</term>
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<front><div type="abstract" xml:lang="en">An investigation of thiophene boronates has revealed the usefulness of a metalation reaction in the synthesis of various lithiated thiophene boronates, which were further converted to functionalized thiopheneboronic derivatives. The lithiation of 2‐ and 3‐thienylboronic N‐butyldiethanolamine (BDEA) esters with lithium diisopropylamide and lithium 2,2,6,6‐tetramethylpiperidide showed that both boronated thiophenes were readily deprotonated. In the latter case, lithiation at the 2‐position adjacent both to sulfur and the borocanyl group is thermodynamically favoured due to the significant stabilizing effect of the borocanyl group. Further derivatization with a range of electrophiles followed by hydrolysis afforded various 2‐substituted 3‐thiopheneboronic acids. Lithiation of the corresponding thiopheneboronic “ate” complexes of the type [ThB(OR)3]Li revealed that the 2‐thienyl derivatives could not be effectively deprotonated, whereas the “ate” complex, [3‐ThB(OEt)3]Li, was selectively lithiated with nBuLi at C‐2. This points to a directing effect of the anionic boronate moiety. The resulting bimetallic species, [(2‐Li‐3‐Th)B(OEt)3]Li, underwent ring‐closing dimerization upon heating to give, after subsequent hydrolysis, 4,8‐dihydro‐4,8‐dihydroxy‐p‐diborino[2,3‐b:5,6‐b′]dithiophene ― a cyclic diborinic acid. A computational study of the lithiation of boronated thiophenes and furans proved that boronation decreases ring‐proton acidity. This effect is much stronger for the boronic “ate” complexes than for the corresponding neutral BDEA esters. Calculations of the transition states have shown that the specific directing effect of boronate groups in 3‐thienyl derivatives is due to intramolecular oxygen–lithium coordination.</div>
</front>
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On the Directing Effect of Boronate Groups in the Lithiation of Boronated Thiophenes

On the Directing Effect of Boronate Groups in the Lithiation of Boronated Thiophenes

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Abstract

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