Synthesis of Homochiral Co<sup>III</sup>– and Mn<sup>IV</sup>–[2.2]Paracyclophane Schiff Base Complexes with Predetermined Chirality at the Metal Centre

Loits, Darran A.; Bräse, Stefan; North, Andrea J.; White, Jonathan M.; Donnelly, Paul S.; Rizzacasa, Mark A.

doi:10.1002/ejic.201600750

Cited by 3 publications

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“…Hydrazides and carbohydrazides have been described as useful building blocks for the assembly of various heterocyclic rings [5]. A large number of aliphatic, alicyclic, aromatic and heterocyclic carbohydrazides [6][7][8][9], their derivatives, and related compounds are reported to present a plethora of biological activities [10][11][12][13][14][15][16].…”

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confidence: 99%

Synthesis of New Planar-Chiral Linked [2.2]Paracyclophanes-N-([2.2]-Paracyclophanylcarbamoyl)-4-([2.2]Paracyclophanylcarboxamide, [2.2]Paracyclophanyl-Substituted Triazolthiones and -Substituted Oxadiazoles

et al. 2020

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The manuscript describes the synthesis of new racemic and chiral linked paracyclophane assigned as N-5-(1,4(1,4)-dibenzenacyclohexaphane-12-yl)carbamoyl)-5’-(1,4(1,4)-dibenzenacyclohexaphane-12-yl)carboxamide. The procedure depends upon the reaction of 5-(1,4(1,4)-dibenzenacyclohexaphane-12-yl)hydrazide with 5-(1,4(1,4)-dibenzenacyclohexaphane-12-yl)isocyanate. To prepare the homochiral linked paracyclophane of a compound, the enantioselectivity of 5-(1,4(1,4)-dibenzenacyclohexaphane-12-yl)carbaldehyde (enantiomeric purity 60% ee), was oxidized to the corresponding acid, which on chlorination, gave the corresponding acid chloride of [2.2]paracyclophane. Following up on the same procedure applied for the preparation of racemic-carbamoyl and purified by HPLC purification, we succeeded to obtain the target Sp-Sp-N-5-(1,4(1,4)-dibenzenacyclohexaphane-12-yl)carbamoyl)-5’-(1,4(1,4)-dibenzenacyclohexaphane-12-yl)carboxamide. Subjecting N-5-(1,4(1,4)-dibenzenacyclohexaphane-12-yl)hydrazide to various isothiocyanates, the corresponding paracyclophanyl-acylthiosemicarbazides were obtained. The latter compounds were then cyclized to a new series of 5-(1,4(1,4)-dibenzenacyclohexaphane-12-yl)-2,4-dihydro-3H-1,2,4-triazol-3-thiones. 5-(1,4(1,4)-Dibenzenacyclohexaphane-12-yl)-1,3,4-oxadiazol-2-amines were also synthesized in good yields via internal cyclization of the same paracyclophanyl-acylthiosemicarbazides. NMR, IR, and mass spectra (HRMS) were used to elucidate the structure of the obtained products. The X-ray structure analysis was also used as an unambiguous tool to elucidate the structure of the products.

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Section: Introductionmentioning

confidence: 99%

Synthesis of New Planar-Chiral Linked [2.2]Paracyclophanes-N-([2.2]-Paracyclophanylcarbamoyl)-4-([2.2]Paracyclophanylcarboxamide, [2.2]Paracyclophanyl-Substituted Triazolthiones and -Substituted Oxadiazoles

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Acetylacetonato cobalt(III) and iron(III) complexes of picolylamine- and aminopropylamine-bis(phenolate) ligands: Synthesis, characterization and crystal structures

et al. 2019

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The reaction between [M(acac)3] (M = Fe, Co, acac = acetylacetonate) and the diamino-bis(phenol) proligands (2-OH-3,5t Bu2-C6H2CH2)2NCH2(2-NC5H4) (H21) and (2-OH-5t Bu-C6H3CH2)2NCH2CH2CH2N(CH3)2 (H22) afforded the [κ 4-(N2,O2)M(acac)] complexes [Fe(1)(acac)] (3), [Fe(2)(acac)] (4), [Co(1)(acac)] (5) and [Co(2)(acac)] (6) in moderate yields after crystallization. The proposed formulas were supported by various analytical data (ESI-MS, FT-IR, EA, NMR), and the molecular structure of all complexes was confirmed by X-ray diffraction studies. In each octahedral complex, the diamino-bis(phenolate) ligand (1 or 2) acts as a tetradentate ligand and the coordination sphere is completed by one chelating κ 2-O2 acac ligand. Although the previously reported ligand 1 and the new ligand 2 are very similar, their coordination to the Fe III (acac) or Co III (acac) moieties varies by the arrangement of the donor atoms. While the Ophenolate donor atoms of ligand 1 were found cis to each other in the Fe III complex 3, they are trans in the Co III complex 5, and vice versa for ligand 2. Since each ligand, 1 and 2, exhibits both configuration, this structural curiosity cannot be easily explained on the basis of steric factors, i.e. ortho-substituents or N,N'-linker length.

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An effectivecis-β-octahedral Mn(iii) SALPN catalyst for the Mukaiyama–Isayama hydration of α,β-unsaturated esters

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Synthesis of Homochiral Co^III– and Mn^IV–[2.2]Paracyclophane Schiff Base Complexes with Predetermined Chirality at the Metal Centre

Abstract: The planar chiral Schiff base ligand 2, derived from (R p )-5-formyl-4-hydroxy-[2.2]paracyclophane (FHPC) (1), was utilised to form a Λ-Co III cis--octahedral metal complex 3 with [a]

Cited by 3 publications

References 28 publications

Synthesis of New Planar-Chiral Linked [2.2]Paracyclophanes-N-([2.2]-Paracyclophanylcarbamoyl)-4-([2.2]Paracyclophanylcarboxamide, [2.2]Paracyclophanyl-Substituted Triazolthiones and -Substituted Oxadiazoles

Synthesis of New Planar-Chiral Linked [2.2]Paracyclophanes-N-([2.2]-Paracyclophanylcarbamoyl)-4-([2.2]Paracyclophanylcarboxamide, [2.2]Paracyclophanyl-Substituted Triazolthiones and -Substituted Oxadiazoles

Acetylacetonato cobalt(III) and iron(III) complexes of picolylamine- and aminopropylamine-bis(phenolate) ligands: Synthesis, characterization and crystal structures

An effectivecis-β-octahedral Mn(iii) SALPN catalyst for the Mukaiyama–Isayama hydration of α,β-unsaturated esters

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Synthesis of Homochiral CoIII– and MnIV–[2.2]Paracyclophane Schiff Base Complexes with Predetermined Chirality at the Metal Centre

Abstract: The planar chiral Schiff base ligand 2, derived from (R p )-5-formyl-4-hydroxy-[2.2]paracyclophane (FHPC) (1), was utilised to form a Λ-Co III cis--octahedral metal complex 3 with [a]

Cited by 3 publications

References 28 publications

Synthesis of New Planar-Chiral Linked [2.2]Paracyclophanes-N-([2.2]-Paracyclophanylcarbamoyl)-4-([2.2]Paracyclophanylcarboxamide, [2.2]Paracyclophanyl-Substituted Triazolthiones and -Substituted Oxadiazoles

Synthesis of New Planar-Chiral Linked [2.2]Paracyclophanes-N-([2.2]-Paracyclophanylcarbamoyl)-4-([2.2]Paracyclophanylcarboxamide, [2.2]Paracyclophanyl-Substituted Triazolthiones and -Substituted Oxadiazoles

Acetylacetonato cobalt(III) and iron(III) complexes of picolylamine- and aminopropylamine-bis(phenolate) ligands: Synthesis, characterization and crystal structures

An effectivecis-β-octahedral Mn(iii) SALPN catalyst for the Mukaiyama–Isayama hydration of α,β-unsaturated esters

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Synthesis of Homochiral Co^III– and Mn^IV–[2.2]Paracyclophane Schiff Base Complexes with Predetermined Chirality at the Metal Centre