Design and synthesis of quasi-diastereomeric molecules with unchanging central, regenerating axial and switchable helical chirality via cleavage and formation of Ni(II)–O and Ni(II)–N coordination bonds

We describe herein the design and synthesis of asymmetric, pentadentate ligands, which are able to coordinate to Ni(II) cations leading to quasi-diastereomeric complexes displaying two new elements of chirality: stereogenic axis and helix along with configurational stabilization of the stereogenic c...

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Main Authors:	Vadim A. Soloshonok, José Luis Aceña, Hisanori Ueki, Jianlin Han
Format:	Article
Language:	English
Published:	Beilstein-Institut 2012-11-01
Series:	Beilstein Journal of Organic Chemistry
Subjects:	axial chirality central chirality chiral switches coordination bonds functional materials helical chirality modular structural design molecular devices
Online Access:	https://doi.org/10.3762/bjoc.8.223

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spelling	doaj-314a8cc88079453a9d7e0a2ca75124dc2021-03-02T11:05:06ZengBeilstein-InstitutBeilstein Journal of Organic Chemistry1860-53972012-11-01811920192810.3762/bjoc.8.2231860-5397-8-223Design and synthesis of quasi-diastereomeric molecules with unchanging central, regenerating axial and switchable helical chirality via cleavage and formation of Ni(II)–O and Ni(II)–N coordination bondsVadim A. Soloshonok0José Luis Aceña1Hisanori Ueki2Jianlin Han3Department of Organic Chemistry I, Faculty of Chemistry, University of the Basque Country, 20018 San Sebastián, SpainDepartment of Organic Chemistry I, Faculty of Chemistry, University of the Basque Country, 20018 San Sebastián, SpainInternational Center for Materials Nanoarchitectonics (MANA), National Institute for Materials Science (NIMS), 1-1, Namiki, Tsukuba, Ibaraki 305-0044, JapanSchool of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210093, ChinaWe describe herein the design and synthesis of asymmetric, pentadentate ligands, which are able to coordinate to Ni(II) cations leading to quasi-diastereomeric complexes displaying two new elements of chirality: stereogenic axis and helix along with configurational stabilization of the stereogenic center on the nitrogen. Due to the stereocongested structural characteristics of the corresponding Ni(II) complexes, the formation of quasi-diastereomeric products is highly stereoselective providing formation of only two, (Ra,Mh,Rc) and (Ra,Ph,Rc), out of the four possible stereochemical combinations. The reversible quasi-diastereomeric transformation between the products (Ra,Mh,Rc) and (Ra,Ph,Rc) occurs by intramolecular trans-coordination of Ni–NH and Ni–O bonds providing a basis for a chiral switch model.https://doi.org/10.3762/bjoc.8.223axial chiralitycentral chiralitychiral switchescoordination bondsfunctional materialshelical chiralitymodular structural designmolecular devices
collection	DOAJ
language	English
format	Article
sources	DOAJ
author	Vadim A. Soloshonok José Luis Aceña Hisanori Ueki Jianlin Han
spellingShingle	Vadim A. Soloshonok José Luis Aceña Hisanori Ueki Jianlin Han Design and synthesis of quasi-diastereomeric molecules with unchanging central, regenerating axial and switchable helical chirality via cleavage and formation of Ni(II)–O and Ni(II)–N coordination bonds Beilstein Journal of Organic Chemistry axial chirality central chirality chiral switches coordination bonds functional materials helical chirality modular structural design molecular devices
author_facet	Vadim A. Soloshonok José Luis Aceña Hisanori Ueki Jianlin Han
author_sort	Vadim A. Soloshonok
title	Design and synthesis of quasi-diastereomeric molecules with unchanging central, regenerating axial and switchable helical chirality via cleavage and formation of Ni(II)–O and Ni(II)–N coordination bonds
title_short	Design and synthesis of quasi-diastereomeric molecules with unchanging central, regenerating axial and switchable helical chirality via cleavage and formation of Ni(II)–O and Ni(II)–N coordination bonds
title_full	Design and synthesis of quasi-diastereomeric molecules with unchanging central, regenerating axial and switchable helical chirality via cleavage and formation of Ni(II)–O and Ni(II)–N coordination bonds
title_fullStr	Design and synthesis of quasi-diastereomeric molecules with unchanging central, regenerating axial and switchable helical chirality via cleavage and formation of Ni(II)–O and Ni(II)–N coordination bonds
title_full_unstemmed	Design and synthesis of quasi-diastereomeric molecules with unchanging central, regenerating axial and switchable helical chirality via cleavage and formation of Ni(II)–O and Ni(II)–N coordination bonds
title_sort	design and synthesis of quasi-diastereomeric molecules with unchanging central, regenerating axial and switchable helical chirality via cleavage and formation of ni(ii)–o and ni(ii)–n coordination bonds
publisher	Beilstein-Institut
series	Beilstein Journal of Organic Chemistry
issn	1860-5397
publishDate	2012-11-01
description	We describe herein the design and synthesis of asymmetric, pentadentate ligands, which are able to coordinate to Ni(II) cations leading to quasi-diastereomeric complexes displaying two new elements of chirality: stereogenic axis and helix along with configurational stabilization of the stereogenic center on the nitrogen. Due to the stereocongested structural characteristics of the corresponding Ni(II) complexes, the formation of quasi-diastereomeric products is highly stereoselective providing formation of only two, (Ra,Mh,Rc) and (Ra,Ph,Rc), out of the four possible stereochemical combinations. The reversible quasi-diastereomeric transformation between the products (Ra,Mh,Rc) and (Ra,Ph,Rc) occurs by intramolecular trans-coordination of Ni–NH and Ni–O bonds providing a basis for a chiral switch model.
topic	axial chirality central chirality chiral switches coordination bonds functional materials helical chirality modular structural design molecular devices
url	https://doi.org/10.3762/bjoc.8.223
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Design and synthesis of quasi-diastereomeric molecules with unchanging central, regenerating axial and switchable helical chirality via cleavage and formation of Ni(II)–O and Ni(II)–N coordination bonds

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