1,6-Interactions between dimethylamino and aldehyde groups in two biphenyl derivatives

O'Leary, Jane; Wallis, John D.; Wood, Michael L.

doi:10.1107/s0108270101006369

Cited by 7 publications

(7 citation statements)

References 15 publications

(10 reference statements)

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“…The substituted biphenyl compounds were synthesized according to the method developed by Wallis and co-workers for the synthesis of unsubstituted 1 H , a palladium-catalyzed Suzuki coupling reaction . Thus, as shown in Scheme , 2-(dimethylamino)phenylboronic acid 2 was coupled with commercially available 2-bromoaldehydes 3 R in the presence of Na 2 CO 3 as base and a catalytic amount of Pd(PPh 3 ) 4 (0.06–0.12 equiv).…”

Section: Resultsmentioning

confidence: 99%

A Search for X-ray Crystallographic Evidence of n → π* Interactions in a Series of Substituted 2-(Dimethylamino)biphenyl-2′-carboxaldehydes

Breton

Davis

Martin

et al. 2019

Crystal Growth & Design

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There has recently been greater appreciation for the impact that n → π* interactions have on the conformational preferences of molecules in the gas phase, solution, and crystalline form. Earlier studies, both experimental and computational, have demonstrated that suitably placed substituents can affect the extent of these interactions. A thorough understanding of how substituents affect these interactions is necessary for these forces to be potentially utilized as a means of crystal engineering. We synthesized a series of 2-(dimethylamino)biphenyl-2′-carboxaldehydes substituted at the position para to the aldehyde group with substituents ranging in electronic properties from strong electron-withdrawing to strong electron-donating and determined their structures via X-ray crystallography. In all cases, evidence suggests that the conformations adopted in the crystals retained n → π* interactions. However, contrary to computational studies conducted in vacuo, the geometries varied not according to the substituents’ electronic properties (as described by Hammett σp values) as expected but instead according to their steric properties (using Sotomatsu and Fujita’s steric parameters; J. Org. Chem.1989544443; Bull. Chem. Soc. Jpn.1992652343). Calculations on representative molecular clusters demonstrate that the geometries adopted in the crystal form are such that they minimize destabilizing intermolecular steric interactions, while maximizing stabilizing intermolecular dispersive and electrostatic forces. This comes at fairly low energetic cost to the molecules relative to their optimized theoretical in vacuo geometries (generally less than 0.5 kcal/mol) even though it stresses, but does not overwhelm, the intramolecular n → π* interactions.

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Section: Resultsmentioning

confidence: 99%

A Search for X-ray Crystallographic Evidence of n → π* Interactions in a Series of Substituted 2-(Dimethylamino)biphenyl-2′-carboxaldehydes

Breton

Davis

Martin

et al. 2019

Crystal Growth & Design

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“…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. 10 Each Suzuki reaction could be carried out smoothly in the presence of tetrakis(triphenylphosphine)palladium as catalyst (Schemes 1 and 2). In the pyridazinone series, chloropyridazinones were conveniently used instead of the less readily available and more expensive bromo derivatives, since the chloro atom has been found to be sufficiently reactive for Suzuki coupling of pyridazinones, due to the electron-withdrawing properties of the pyridazinone ring.…”

Section: Figurementioning

confidence: 99%

“…11 It is noteworthy that single-crystal X-ray diffraction of aldehyde 7b confirmed a short distance (2.835 Å) 12 between the nitrogen and carbonyl carbon, similarly as found for aldehyde 7c (2.989 Å). 10 We designed three series of vinyl derivatives, one series with acyclic and two with cyclic vinyl substituents. First, dicyanomethylene compounds were targeted as 'gold standard'.…”

Section: Figurementioning

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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“…8 It is immediately recognizable that the structures of the molecules fall into two groups, one (for 2-5) with long Me 2 N----sp 2 C separations in the range 2.929(3) -3.029(3) Å comparable to the 1,5 N---C=O interaction in methadone 10 (2.912(3) Å), 9 and the other 50 (for 6 and 7) in which, remarkably, there has been bond formation between the groups to give zwitterionic structures 8 and 9. In no case do the functional groups in these cases choose to avoid an intramolecular interaction or reaction.…”

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confidence: 99%

Interactions and reactions in some 2,2′-disubstituted biphenyls—an open or shut case

O'Leary

Wallis

2009

Org. Biomol. Chem.

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1,6-Interactions between dimethylamino and aldehyde groups in two biphenyl derivatives

Cited by 7 publications

References 15 publications

A Search for X-ray Crystallographic Evidence of n → π* Interactions in a Series of Substituted 2-(Dimethylamino)biphenyl-2′-carboxaldehydes

A Search for X-ray Crystallographic Evidence of n → π* Interactions in a Series of Substituted 2-(Dimethylamino)biphenyl-2′-carboxaldehydes

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

Interactions and reactions in some 2,2′-disubstituted biphenyls—an open or shut case

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