Control of asymmetric biaryl conformations with terpenol moieties: Syntheses, structures and energetics of new enantiopure C2-symmetric diols
New enantiopure, C2-symmetric biphenyl-2,2′-diols based on (−)-menthone (BIMOL), (−)-verbenone (BIVOL) and (−)-carvone (BICOL and hydrogenated BIMEOL), are accessible via short, synthetic routes. All diols form intramolecular hydrogen bonds and hence can be employed as chelating ligands for catalyst...
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| Format: | Article |
| Language: | English |
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Beilstein-Institut
2008-07-01
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| Series: | Beilstein Journal of Organic Chemistry |
| Subjects: | |
| Online Access: | https://doi.org/10.3762/bjoc.4.25 |
| _version_ | 1818413269520482304 |
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| author | Y. Alpagut B. Goldfuss J.-M. Neudörfl |
| author_facet | Y. Alpagut B. Goldfuss J.-M. Neudörfl |
| author_sort | Y. Alpagut |
| collection | DOAJ |
| description | New enantiopure, C2-symmetric biphenyl-2,2′-diols based on (−)-menthone (BIMOL), (−)-verbenone (BIVOL) and (−)-carvone (BICOL and hydrogenated BIMEOL), are accessible via short, synthetic routes. All diols form intramolecular hydrogen bonds and hence can be employed as chelating ligands for catalyst design, as it demonstrated for the (−)-fenchone based BIFOL. The sense of asymmetry of the biphenyl axes is controlled by the chiral terpene units and is conformationally surprisingly stable. X-ray analyses reveal M biphenyl conformation for BIMOL and P biphenyl conformation for each of BIVOL, BICOL and BIMEOL. The origins of the conformational biphenyl preferences are confirmed by computational ONIOM evaluations of the diols and their diastereomeric conformers. The experimentally observed biphenyl conformations are all energetically preferred, i.e. with 1.3 kcal/mol for (M)-BIMOL, with 5.1 kcal/mol for (P)-BIVOL, with 5.8 kcal/mol for (P)-BICOL, and with 5.4 kcal/mol for (P)-BIMEOL. |
| first_indexed | 2024-12-14T11:00:31Z |
| format | Article |
| id | doaj.art-7cf4db9c28f145ca936d284d8e21f5d2 |
| institution | Directory Open Access Journal |
| issn | 1860-5397 |
| language | English |
| last_indexed | 2024-12-14T11:00:31Z |
| publishDate | 2008-07-01 |
| publisher | Beilstein-Institut |
| record_format | Article |
| series | Beilstein Journal of Organic Chemistry |
| spelling | doaj.art-7cf4db9c28f145ca936d284d8e21f5d22022-12-21T23:04:44ZengBeilstein-InstitutBeilstein Journal of Organic Chemistry1860-53972008-07-01412510.3762/bjoc.4.251860-5397-4-25Control of asymmetric biaryl conformations with terpenol moieties: Syntheses, structures and energetics of new enantiopure C2-symmetric diolsY. Alpagut0B. Goldfuss1J.-M. Neudörfl2Institut für Organische Chemie, Universität zu Köln, Greinstrasse 4, D-50939 Köln, Germany. Fax: +49(0)221-470-5057, http://www.uni-koeln.de/goldfuss.Institut für Organische Chemie, Universität zu Köln, Greinstrasse 4, D-50939 Köln, Germany. Fax: +49(0)221-470-5057, http://www.uni-koeln.de/goldfuss.Institut für Organische Chemie, Universität zu Köln, Greinstrasse 4, D-50939 Köln, Germany. Fax: +49(0)221-470-5057, http://www.uni-koeln.de/goldfuss.New enantiopure, C2-symmetric biphenyl-2,2′-diols based on (−)-menthone (BIMOL), (−)-verbenone (BIVOL) and (−)-carvone (BICOL and hydrogenated BIMEOL), are accessible via short, synthetic routes. All diols form intramolecular hydrogen bonds and hence can be employed as chelating ligands for catalyst design, as it demonstrated for the (−)-fenchone based BIFOL. The sense of asymmetry of the biphenyl axes is controlled by the chiral terpene units and is conformationally surprisingly stable. X-ray analyses reveal M biphenyl conformation for BIMOL and P biphenyl conformation for each of BIVOL, BICOL and BIMEOL. The origins of the conformational biphenyl preferences are confirmed by computational ONIOM evaluations of the diols and their diastereomeric conformers. The experimentally observed biphenyl conformations are all energetically preferred, i.e. with 1.3 kcal/mol for (M)-BIMOL, with 5.1 kcal/mol for (P)-BIVOL, with 5.8 kcal/mol for (P)-BICOL, and with 5.4 kcal/mol for (P)-BIMEOL.https://doi.org/10.3762/bjoc.4.25chiral diolshydrogen bondsaxial chiralityterpenes |
| spellingShingle | Y. Alpagut B. Goldfuss J.-M. Neudörfl Control of asymmetric biaryl conformations with terpenol moieties: Syntheses, structures and energetics of new enantiopure C2-symmetric diols Beilstein Journal of Organic Chemistry chiral diols hydrogen bonds axial chirality terpenes |
| title | Control of asymmetric biaryl conformations with terpenol moieties: Syntheses, structures and energetics of new enantiopure C2-symmetric diols |
| title_full | Control of asymmetric biaryl conformations with terpenol moieties: Syntheses, structures and energetics of new enantiopure C2-symmetric diols |
| title_fullStr | Control of asymmetric biaryl conformations with terpenol moieties: Syntheses, structures and energetics of new enantiopure C2-symmetric diols |
| title_full_unstemmed | Control of asymmetric biaryl conformations with terpenol moieties: Syntheses, structures and energetics of new enantiopure C2-symmetric diols |
| title_short | Control of asymmetric biaryl conformations with terpenol moieties: Syntheses, structures and energetics of new enantiopure C2-symmetric diols |
| title_sort | control of asymmetric biaryl conformations with terpenol moieties syntheses structures and energetics of new enantiopure c2 symmetric diols |
| topic | chiral diols hydrogen bonds axial chirality terpenes |
| url | https://doi.org/10.3762/bjoc.4.25 |
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