Please use this identifier to cite or link to this item:
|Title:||Organopalladium complex promoted asymmetric cycloaddition reactions involving 3,4-dimethyl-1-phenylphosphole 1-sulfide as the heterocyclic diene||Authors:||Qin, Y.
|Issue Date:||25-Nov-2002||Citation:||Qin, Y., Selvaratnam, S., Vittal, J.J., Leung, P.-H. (2002-11-25). Organopalladium complex promoted asymmetric cycloaddition reactions involving 3,4-dimethyl-1-phenylphosphole 1-sulfide as the heterocyclic diene. Organometallics 21 (24) : 5301-5306. ScholarBank@NUS Repository. https://doi.org/10.1021/om020682u||Abstract:||3,4-Dimethy]-l-phenylphosphole 1-sulfide (DMPPS) reacted as a heterocyclic diene in the asymmetric Diels-Alder reaction with diphenylvinylphosphine in the presence of an organopalladium(II) complex derived from the enantiomerically pure ortho-metalated (R)-(l-(dimethylamino)ethy)naphthalene. The cycloaddition reaction proceeded at room temperature via an intramolecular mechanism in which the cyclic diene and the dienophile were coordinated simultaneously on the chiral palladium template. The (Rp)-exo cycloadduct was obtained with high stereoselectivity as a P-S bidentate chelate on the palladium template. When DMPPS was treated with the heterodienophile thiobenzophenone at 50 °C in the presence of the organopalladium(II) complex, the corresponding heterocycloaddition reaction proceeded to generate the expected cycloadduct as a rigid S-S bidentate chelate on the palladium template. However, the cyclic adduct was obtained as a racemic mixture. The low stereoselectivity in the heterocycloaddition reaction is attributed to the kinetic instability of S→Pd coordination bonds in the intermediate template complex. Both the P-S and S-S cycloadducts could be liberated from the corresponding template complexes by treatment of the template complexes with aqueous potassium cyanide.||Source Title:||Organometallics||URI:||http://scholarbank.nus.edu.sg/handle/10635/116503||ISSN:||02767333||DOI:||10.1021/om020682u|
|Appears in Collections:||Staff Publications|
Show full item record
Files in This Item:
There are no files associated with this item.
checked on Aug 14, 2019
WEB OF SCIENCETM
checked on Aug 14, 2019
checked on Aug 16, 2019
Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.