| Yazarlar |
Sebastıan Rendler
|
|
Olıver Plefka
|
Prof. Dr. Betül KARATAŞ
Türkiye |
|
Gertrud Auer
|
|
Roland Fröhlıch
|
|
Chrıstıan Mück Lıchtenfeld
|
|
Stefan Grımme
|
|
Martın Oestreıch
|
| Özet |
| Ligand-stabilized copper(I)hydride catalyzes the dehydrogenative Si-O coupling of alcohols and silanes-a process that was found to proceed without racemization at the silicon atom if asymmetrically substituted. The present investigation starts from this pivotal observation since silicon-stereogenic silanes are thereby suitable for the reagent-controlled kinetic resolution of racemic alcohols, in which asymmetry at the silicon atom enables discrimination of enantiomeric alcohols. In this full account, we summarizeour efforts to systematically examine this unusual strategy of diastereoselective alcohol silylation. Ligand (sufficient reactivity with moderately electron-rich monophosphines), silane (reasonable diastereocontrol with cyclic silanes having a distinct substitution pattern) as well as substrate identification (chelating donor as a requirement) areintroductorily described. With these basic data at hand, the substrate scope was defined employing enantiomerically enriched tert-butyl-substituted 1-silatetraline and highly reactive 1-si-laindane. The synthetic part is complemented by the determination of the stereochemical course at the silicon atom in the Si-O coupling step followed by its quantum-chemical analysis thus providing a solid mechanistic picture of this remarkable transformation. © 2008 Wiley-VCH Verlag GmbH & Co. KGaA. |
| Anahtar Kelimeler |
| Alcohols asymmetric catalysis | Copper | Kinetic resolution | Silicon |
| Makale Türü | Özgün Makale |
| Makale Alt Türü | SSCI, AHCI, SCI, SCI-Exp dergilerinde yayımlanan tam makale |
| Dergi Adı | Chemistry - A European Journal |
| Dergi ISSN | 0947-6539 |
| Dergi Tarandığı Indeksler | SSCI |
| Makale Dili | İngilizce |
| Basım Tarihi | 11-2008 |
| Cilt No | 14 |
| Sayı | 36 |
| Sayfalar | 11512 / 11528 |
| Doi Numarası | 10.1002/chem.200801377 |
| Makale Linki | http://doi.wiley.com/10.1002/chem.200801377 |
| Atıf Sayıları | |
| SCOPUS | 76 |
| Google Scholar | 106 |
