Arylboronic acids with intramolecular B–N interaction: convenient synthesis through ortho-lithiation of substituted benzylamines

Lauer, M.; Wulff, Günter

doi:10.1016/s0022-328x(00)99290-8

Cited by 75 publications

(31 citation statements)

References 33 publications

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“…Other important studies incorporate the boronic acid moiety into amino acids and nucleosides as antitumor and antiviral agents [3–4]. Indeed, the great importance of aromatic boronic acids to biological and pharmaceutical purposes has been reported, as well as the interest to introduce a boronic acid moiety in organic molecules [5]. Boron has been shown to bind with nitrogen in order to form a ring in 2-( N , N -dimethylaminomethyl)phenylboronic acid [6], thus reflecting its electron acceptor ability through intramolecular interactions.…”

Section: Introductionmentioning

confidence: 99%

Conformational analysis and intramolecular interactions in monosubstituted phenylboranes and phenylboronic acids

Silla¹,

Cormanich²,

Rittner³

et al. 2013

Beilstein J. Org. Chem.

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SummaryA 1 TS J F,H(O) coupling pathway, dictated by a hydrogen bond, in some 2-fluorobenzoic acids has been observed, while such an interaction does not occur in 2-fluorophenol. Thus, this work reports the conformational analysis of 2-fluorophenylboronic acid (1), in order to evaluate a possible intramolecular OH∙∙∙F hydrogen bond in comparison to an nF→pB interaction, which mimics the quantum nF→σ*OH hydrogen bond that would be expected in 2-fluorophenol. 2-Fluorophenylborane (3), which does not experience hydrogen bonding, was used to verify whether nF→pB interaction governs the conformational equilibrium in 1 due to a predominant OH∙∙∙F hydrogen bond or to other effects. A series of 2-X-phenylboranes (X = Cl, Br, NH2, PH2, OH and SH) were further computationally analyzed to search for electron donors to boron, capable of influencing the conformational equilibrium. Overall, the intramolecular OH∙∙∙F hydrogen bond in 1 is quite stabilizing and dictates the 1 h J F,H(O) coupling constant. Moreover, electron donation to the empty p orbital of boron (for noncoplanar BH2 moiety relative to the phenyl ring) is also significantly stabilizing for the NH2 and PH2 derivatives, but not enough to make the corresponding conformers appreciably populated, because of steric effects and the loss of πCC→pB resonance. Thus, the results found earlier for 2-fluorophenol about the lack of intramolecular hydrogen bonding are now corroborated.

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Section: Introductionmentioning

confidence: 99%

Conformational analysis and intramolecular interactions in monosubstituted phenylboranes and phenylboronic acids

Silla¹,

Cormanich²,

Rittner³

et al. 2013

Beilstein J. Org. Chem.

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“…Isomerization of o-(o-vinylaryl)aryl-tert-amines may lead through nitrogen-carbon or carbon-carbon bond formation to novel types of phenanthridines or diarene-fused azocines, respectively. The latter transformation may proceed through [1,7]-hy- drogen migration or hydride transfer. The X-ray analysis demonstrated that the tert-amino and vinyl groups of o-(ovinylaryl)aryl-tert-amines are located on the same face of the biaryl system, and their distances from each other indicate a weak interaction between them via a tert-amino effect.…”

Section: Methodsmentioning

confidence: 99%

“…Accordingly, we took two different types of Suzuki reactions into account for this step, using either o-formylboronic acid or o-(dialkylamino)boronic acid. 7 The choice of the required reagents was based on their availability and reactivity. Aldehydes 7a,b and 12a-c were prepared from commercially available o-formylphenylboronic acid with easily obtainable o-haloarylamines 6a,b 8 and 11a-c 9 (Tables 1 and 2), respectively, whereas aldehyde 7c was synthesized through the known reaction of o-(dimethylamino)phenylboronic acid with o-bromobenzaldehyde.…”

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confidence: 99%

“…12 The phenanthridinium derivatives are presumably first transformed to the vinyl compounds, which isomerize to the dibenzofused system in two steps. In the rate-limiting first step, a dipolar intermediate is formed via either antarafacial [1,7]-hydrogen migration or, more probably, hydride anion transfer, and in the next step the intermediate cyclizes to the fused ring system (Scheme 7).…”

mentioning

confidence: 99%

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Novel Extensions of the tert-Amino Effect: Formation of Phenanthridines and Diarene-Fused Azocines from ortho-ortho′-Functionalized Biaryls

Polonka‐Balint¹,

Saraceno²,

Ludányi³

et al. 2008

Synlett

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Novel Extensions of the tert-Amino Effect: Formation of Phenanthridines and Diarene-Fused Azocines from ortho-ortho′-Functionalized Biaryls F o r m a t i o n o f P h e n a n t h r i d i n e s a n d D i a r e n e -F u s e d A z o c i n e s This work is kindly dedicated to Prof. László Tőke on the occasion of his 75 th birthday.Abstract: Phenanthridines and azocines fused to two benzene rings or one benzene and one pyridazinone ring, which are otherwise difficult to access, were prepared via two new extensions of the tertamino effect. The synthetic pathway includes three steps: i) Suzuki reaction of an ortho-functionalized phenylboronic acid with orthodisubstituted benzenes or pyridazinones; ii) the Knoevenagel condensation reaction of the biaryl aldehydes formed with active methylene compounds to obtain vinyl derivatives or, through their cyclization, phenanthridines via a tert-amino effect; and iii) thermal isomerization of vinyl or phenanthridinium compounds to fused azocines via another type of tert-amino effect.

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“…Due to the robustness of these approaches, we felt that they would be ideally suited for incorporation of free boronic acids into polycarbonate backbones. This would allow for the direct incorporation of important functional boronic acids such as Wulff-type boronates, which are frequently used in material and sensing applications. − , These types of boronic acid containing polycarbonates would otherwise be inaccessible via traditional de novo monomer synthesis and polymerization. To accomplish this, we prepared several different polycarbonates that could be utilized as starting materials to access neutral or cationic boronic acid functionalized polycarbonate scaffolds (Figure ).…”

mentioning

confidence: 99%

Convergent Approach to Boronic Acid Functionalized Polycarbonates: Accessing New Dynamic Material Platforms

et al. 2017

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Polycarbonates are routinely utilized for diverse medicinal applications and are highly efficacious scaffolds for drug delivery and antimicrobial treatments. In order to provide for robust, dynamic platforms for biomedical applications, we have developed new routes for the incorporation of boronic acids into the polycarbonate backbone. These routes take advantage of straightforward postsynthesis modification of established polycarbonate backbones, enabling the preparation of a diverse array of boronic acid functionalized polycarbonates from readily accessible polycarbonates. In particular, this approach circumvents the need for de novo monomer synthesis, functional group incompatibilities, and deprotection steps that often limit other methods. This strategy has been demonstrated using a broad array of unprotected boronic acids to produce both neutral and cationic boronic acid functionalized polycarbonates.

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Arylboronic acids with intramolecular B–N interaction: convenient synthesis through ortho-lithiation of substituted benzylamines

Cited by 75 publications

References 33 publications

Conformational analysis and intramolecular interactions in monosubstituted phenylboranes and phenylboronic acids

Conformational analysis and intramolecular interactions in monosubstituted phenylboranes and phenylboronic acids

Novel Extensions of the tert-Amino Effect: Formation of Phenanthridines and Diarene-Fused Azocines from ortho-ortho′-Functionalized Biaryls

Convergent Approach to Boronic Acid Functionalized Polycarbonates: Accessing New Dynamic Material Platforms

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