Synthesis of novel enantiomerically pure trianglimine and trianglamine macrocycles

Kuhnert, Nikolai; Strassnig, Christian; López‐Periago, Ana M.

doi:10.1016/s0957-4166(02)00065-4

Cited by 68 publications

(45 citation statements)

References 16 publications

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“…The all-R enantiomer of 4 has been previously reported by Gawronski and co-workers 17 and the all-R enantiomer of compound 5 by our group. 10 The spectroscopic properties of the trianglamine macrocycles were as expected and are given in the experimental section. With both enantiomers of the trianglimine macrocycles 4 and 5 in hand we obtained the unlabelled compounds by reduction with NaBH 4 and their quasienantiomeric deuterated counterparts by reduction with NaBD 4 , respectively, in excellent yields.…”

Section: Synthesis Of Triangliminessupporting

confidence: 58%

“…[10][11][12][13][14][15] In the course of our investigation we observed frequently that under ESI mass spectrometric conditions the homochiral macrocycles did assemble in the gas phase into larger clusters. Since trianglamines are readily available in both enantiomeric forms we decided to investigate the chiroselection of this self-assembly process in detail and report the finding of our studies in this publication.…”

Section: -9mentioning

confidence: 63%

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Synthesis, self‐association and chiroselectivity of isotopically labeled trianglamine macrocycles in the ion trap mass spectrometer

Kuhnert

LeGresley

Nicolau

et al. 2007

Labelled Comp Radiopharmac

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Abstract:The synthesis and self-association of chiral isotopically labeled trianglamine macrocycles under electrospray mass spectrometer conditions in an ion trap are described. A moderate diastereoselectivity in the self-association process was observed providing a synthetic model system for the investigation of chiral selfassociation in the gas phase. The first non-covalently bound dimer exclusively bonded through aromatic-aromatic interactions was observed in the gas phase. Evidence for self-association in solution was observed by diffusion nuclear magnetic resonance spectroscopy. Copyright # 2007 John Wiley & Sons, Ltd.Keywords: deuterium labeling; supramolecular chemistry; mass spectrometry; chiral recognition; macrocyclic chemistry Molecular recognition is an area of chemistry aiming at the understanding of complementarity of size shape and functionality at the supramolecular level. It explores weak interaction between two or more molecules over short distances resulting in complex molecular assemblies.1,2 At this supramolecular level chirality can be expressed through the diastereoselective formation of molecular clusters through selfassembly of homochiral building blocks. 3,4 Mass spectrometry has been shown to provide an experimental technique suitable for the study of these diastereoselective self-assembly processes in the gas phase. Early reports demonstrated the self-association of homochiral tartrate derivatives in the gas phase. 5,6 Most prominently homochiral amino acids, in particular serine, were reported to form non-covalent clusters readily generated by electrospraying or sublimation and observed and characterized through ESI mass spectrometry. 7-9Studies on such chiral supramolecules have been motivated to a large extent by the possibility that such self-assembled clusters of homochiral molecules play an important role in the origin of homochirality in biological systems, exemplified by the preference of amino acids for the l-configuration or sugars for the d-configuration.Our group has studied for some time the chemistry of homochiral polyamine and polyimine macrocycles, which we named trianglimines and trianglamines. [10][11][12][13][14][15] In the course of our investigation we observed frequently that under ESI mass spectrometric conditions the homochiral macrocycles did assemble in the gas phase into larger clusters. Since trianglamines are readily available in both enantiomeric forms we decided to investigate the chiroselection of this self-assembly process in detail and report the finding of our studies in this publication. Results and discussions Synthesis of triangliminesFor our studies concerned with the chiroselection of homochiral trianglamine macrocycles through mass spectrometry we required macrocycles in both enantiomeric forms that were isotopically labelled in order to distinguish between diastereomeric clusters in the mass spectrometer. If one of either enantiomers of a given compound is isotopically labelled the two

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Section: Synthesis Of Triangliminessupporting

confidence: 58%

Section: -9mentioning

confidence: 63%

Synthesis, self‐association and chiroselectivity of isotopically labeled trianglamine macrocycles in the ion trap mass spectrometer

Kuhnert

LeGresley

Nicolau

et al. 2007

Labelled Comp Radiopharmac

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“…For the present study we have selected trianglimine 1 [30] trianglamines 2, 3, [30,31] 4, [32,33] and rhombamine 5, [34] as well as N,N'-dibenzyl-DACH (6) as a reference ligand.…”

Section: Asymmetric Hydrosilylationmentioning

confidence: 99%

Convenient Enantioselective Hydrosilylation of Ketones Catalyzed by Zinc‐Macrocyclic Oligoamine Complexes

2009

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Chiral macrocyclic tetra-and hexamine macrocycles derived from trans-1,2-diaminocyclohexane (DACH) in complexes with diethylzinc efficiently catalyze the asymmetric hydrosilylation of aryl alkyl ketones with enantiomeric excess of the product up to 89%. The cyclic structure of the trianglamine ligand increases the enantioselectivity of the reaction, in comparison to the catalysis with the acyclic N,N'-dibenzyl-DACH ligand. Density functional theory (DFT) computations on the structures of ligand-zinc complexes and on the structures of these complexes with a coordinated acetophenone molecule allow us to rationalize the direction of the asymmetric induction of the hydrosilylation reaction as well as the superiority of the cyclic ligand compared to the acyclic one. This is the first example of asymmetric catalysis for the hydrosilylation reaction of ketones with the use of a readily available, inexpensive, and reusable macrocyclic trianglamine ligand.

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“…Macrocycles possessing 3, 4, or 8 donor nitrogen atoms and no direct C sp 2-N bond coordinate copper and zinc cations and [PdCl 4 ] 2-anions [90]. More complex biphenyl-based cyclic ligands were synthesized recently [91][92][93][94][95], in particular by palladium-catalyzed reactions involving formation of new carbon-carbon bonds [96].…”

Section: Scheme 15mentioning

confidence: 99%

Palladium-catalyzed amination in the synthesis of polyazamacrocycles

et al. 2010

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The review describes palladium-catalyzed amination of acyclic di-and polyamines with aryl halides with a view to reveal general relations holding in this process. Conditions for the synthesis of macrocycles via catalytic diamination of 1,2-and 1,3-dibromobenzenes, 1,3-dichloro-2-bromobenzene, 2,6-and 3,5-dibromopyridines, 3,3′-and 4,4′-dibromobiphenyls, 2,7-dibromonaphthalene, 1,8-and 1,5-dichloroanthracene, 1,8-and 1,5-dichloroanthraquinones, and bis(haloaryl) derivatives of cyclen, cyclam, and cholanediol are discussed. The possibility for palladium-catalyzed arylation of cyclic polyamines has been demonstrated. Specificity of macrocyclization processes and relations between the yield of macrocycles and the nature of initial compounds are considered, and data on the synthesis of cyclic dimers are given. Applications of polyazamacroheterocycles as optical sensors for metal cations are described using as examples macrocyclic compounds derived from 1,8-disubstituted anthraquinone.

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Synthesis of novel enantiomerically pure trianglimine and trianglamine macrocycles

Cited by 68 publications

References 16 publications

Synthesis, self‐association and chiroselectivity of isotopically labeled trianglamine macrocycles in the ion trap mass spectrometer

Synthesis, self‐association and chiroselectivity of isotopically labeled trianglamine macrocycles in the ion trap mass spectrometer

Convenient Enantioselective Hydrosilylation of Ketones Catalyzed by Zinc‐Macrocyclic Oligoamine Complexes

Palladium-catalyzed amination in the synthesis of polyazamacrocycles

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