13384-54-8Relevant articles and documents
Selective iron-catalyzed cross-coupling reactions of Grignard reagents with enol triflates, acid chlorides, and dichloroarenes
Scheiper, Bodo,Bonnekessel, Melanie,Krause, Helga,Fuerstner, Alois
, p. 3943 - 3949 (2007/10/03)
Cheap, readily available, air stable, nontoxic, and environmentally benign iron salts such as Fe(acac)3 are excellent precatalysts for the cross-coupling of Grignard reagents with alkenyl triflates and acid chlorides. Moreover, it is shown that dichloroarene and -heteroarene derivatives as the substrates can be selectively monoalkylated by this method. All cross-coupling reactions proceed very rapidly under notably mild conditions and turned out to be compatible with a variety of functional groups in both reaction partners. A detailed analysis of the preparative results suggests that iron-catalyzed C-C bond formations can occur via different pathways. Thus, it is likely that reactions of methylmagnesium halides involve iron-ate complexes as the active components, whereas reactions of Grignard reagents with two or more carbon atoms are effected by highly reduced iron-clusters of the formal composition [Fe(MgX)2]n generated in situ. Control experiments using the ate-complex [Me4Fe]Li2 corroborate this interpretation.
A Nickel-catalyzed carbozincation of aryl-substituted alkynes
Stuedemann, Thomas,Ibrahim-Ouali, Malika,Knochel, Paul
, p. 1299 - 1316 (2007/10/03)
The addition of dialkylzincs or diphenylzinc to substituted phenylacetylenes in the presence of catalytic amounts of Ni(acac)2 in THF:NMP mixtures produces syn-carbozincation products with good to excellent regio- and stereoselectivity. After quenching with an electrophile (iodine, acyl chloride, allyl bromide) tetrasubstituted olefines are obtained in good to satisfactory yields. An intramolecular version of the reaction is possible using a terminal triple bond bearing an iodine at a remote position. More substituted iodo-alkynes furnish only reductive elimination products. An application to a stereoselective synthesis of (Z)-tamoxifen (Z:E > 99:1) has been developed.
A Dynamic Equilibrium of Oxaphosphetanes
Geletneky, Christian,Foersterling, Frank-Holger,Bock, Willi,Berger, Stefan
, p. 2397 - 2402 (2007/10/02)
The course of the Wittig reaction was investigated by rapid injection NMR spectroscopy.Rate constants for the formation of oxaphosphetanes were determined.A new dynamic equilibrium of oxaphosphetanes was observed for the first time.The solvent and substituent dependence of the new effect was investigated.By labeling various oxaphosphetanes with 13C and 17O the lithium salt dependence of the new equilibrium was shown.A lithium adduct of oxaphosphetanes under these conditions is proposed. - Key Words: Wittig reaction / Rapid injection NMR / Dynamic NMR / Oxaphosphetanes