NUCLEOPHILIC-ATTACK ON YDRO-4-ALKYL-3H-DINAPHTHO[2,1-C-1',2'-E]THIEPINIUM SALTS - A CONVENIENT APPROACH TO NEW 2,2'-BIDENTATE 1,1'-BINAPHTHALENE LIGANDS WITH SULFUR DONOR ATOMS

Citation
Ig. Stara et al., NUCLEOPHILIC-ATTACK ON YDRO-4-ALKYL-3H-DINAPHTHO[2,1-C-1',2'-E]THIEPINIUM SALTS - A CONVENIENT APPROACH TO NEW 2,2'-BIDENTATE 1,1'-BINAPHTHALENE LIGANDS WITH SULFUR DONOR ATOMS, Journal of organic chemistry, 59(6), 1994, pp. 1326-1332
Citations number
31
Categorie Soggetti
Chemistry Inorganic & Nuclear
ISSN journal
00223263
Volume
59
Issue
6
Year of publication
1994
Pages
1326 - 1332
Database
ISI
SICI code
0022-3263(1994)59:6<1326:NOY>2.0.ZU;2-F
Abstract
The title dihydrothiepinium salts 6 react with a wide range of N-, S-, Se-, O-, and C-nucleophiles to afford dihydrothiepin 5 and/or the cor responding bidentate ligands 7. The dual course of the reaction can be controlled by a judicious choice of the substrate counterion. In most instances, an iodide counterion aids formation of dihydrothiepins 5, whereas perchlorate, tetraphenyl borate, or tetrafluoroborate counteri ons favor formation of bidentate ligands 7. An explanation based on a competition between the counterion and the external nucleophile is pro vided. Dihydrothiepinium salts 6 are easily accessible from dibromide (R,S)-4 via dihydrothiepin (R,S)-5. Individual enantiomers (R)- and (S )-5 have been obtained by resolution on a preparative triacetylcellulo se (TAC) column and assigned absolute configuration on the basis of CD spectra and chemical correlation.