MANGANESE-MEDIATED SYNTHESIS OF CIS-DISUBSTITUTED CYCLOHEXADIENES VIADOUBLE NUCLEOPHILIC-ADDITION TO COORDINATED ARENES

Citation
Ty. Lee et al., MANGANESE-MEDIATED SYNTHESIS OF CIS-DISUBSTITUTED CYCLOHEXADIENES VIADOUBLE NUCLEOPHILIC-ADDITION TO COORDINATED ARENES, Inorganica Chimica Acta, 214(1-2), 1993, pp. 125-134
Citations number
48
Language
INGLESE
art.tipo
Article
Categorie Soggetti
Chemistry Inorganic & Nuclear
Journal title
ISSN journal
0020-1693
Volume
214
Issue
1-2
Year of publication
1993
Pages
125 - 134
Database
ISI
SICI code
0020-1693(1993)214:1-2<125:MSOCCV>2.0.ZU;2-N
Abstract
The addition of carbon donor nucleophiles to (arene)Mn(CO)2L+ (L=CO, P (OPh)3, PMe3), followed by replacement of a CO with NO+, affords monof unctionalized (cyclohexadienyl)Mn(CO)(NO)L+ complexes (12). A study ha s been made of nucleophilic addition to 12 to yield cyclohexadiene com plexes (13). The yield of the reaction of 12 with soft stabilized carb on donors (e.g. NaCH(CO2Et)CN) improves substantially when the ligand L=CO is replaced by L=P(OPh)3 or PMe3. Hydride donors give good yields of monofunctionalized cyclohexadiene complexes regardless of the natu re of L. When L not-equal CO, significant chiral discrimination takes place and the product is obtained as a mixture of diastereomers. Oxida tion of the (cyclohexadiene)Mn(CO)(NO)L complexes with FeCl3 or Me3NO generates the free hydrocarbon ligand as cis-disubstituted cyclohexa-1 ,3-dienes or cyclohexen-1-ones, the latter resulting from hydrolysis o f a methoxy substituent. Hard carbon donors such as LiPh and LiMe atta ck a CO in 12, ultimately converting to trans-disubstituted cyclohexad ienes. This work shows that the manganese-mediated double nucleophilic addition to arenes can be an efficient route to functionalized cycloh exadienes.