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
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
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.