Tin–magnesium transmetallation reactions

Alkaline Earth Organometallics

“…Alkylmagnesium amides, in particular, Mg(Bu)NPr i 2 , have been studied as new bases to address this issue. 151 Transmetallations between Bu 3 SnCH 2 YMe 2 (Y ¼ N, P) and MgMe 2 proceeded only in the presence of catalytic amounts (10-20 mol%) of LiBu, yielding Mg(CH 2 YMe 2 )Me and SnBu 3 Me/SnBu 4 . 175 Diorganyl magnesium complexes are used in many syntheses as either a source of magnesium or as ligand-transfer reagents.…”

“…When the Bu 2 Mg : diisopropylamine (DAH) ratio is 1 : 1, cis-b-metallation is favored, but at 2 : 1, a-metallation predominates, indicating that excess Bu 2 Mg scavenges the DAH formed in the initial a-deprotonation, preventing equilibration. 151 The mechanism of chelation-controlled addition reactions of aand b-alkoxy carbonyl compounds (methoxyacetone, methoxyacetaldehyde, 3-methoxy-2-butanone, 2-methoxypropanal, 4-methoxy-2-butanone, 3-methoxypropanal, and 3-methoxybutanal) with MgMe 2 has been investigated with ab initio calculations. A full listing of individual compounds would be prohibitively long, and as many of the products are not organometallic species, they are often discussed in other places, such as CCC (2004).…”

2 Alkali and alkaline-earth metals

“…116 The synthesis and structure of [Mg(n-C 6 H 13 )(O-2,6-Bu t 2 -4-MeC 6 H 2 )] 2 have been reported 117 as have the preparations of [MgCH 2 S(O) n R]X (n = 0, 1 or 2, R = Me or Ph, X = Cl, Br, I, Me or Bu) and [MgCH 2 P(O)Ph 2 ]Br, via Sn-Mg transmetallation. 118 A kinetic study of the reaction of several organomagnesium compounds with ketones has appeared. 119…”

Lithiated γ-O-functionalized propyl phenyl sulfides and sulfones of the type Li[CH(SOxPh)CH2CH2OR] (x=0, 2). [Li{CH(SPh)CH2CH2Ot-Bu}(tmeda)] – A structurally characterized organolithium inner complex

“…On the other hand, the substitution pattern of the a-C atom influences the electronic properties of a-sulfonyl ligands: the 1 J( 119 Sn, 13 C Bu ) coupling constants of the compounds having secondary a-C atoms (329.2-338.9 Hz) lie in-between of those having tertiary (n-Bu 3 SnCMe(Et)SO 2 Ph, 325.6 Hz[25]) and primary (n-Bu 3 SnCH 2 SO 2 Ph, 346.1 Hz[28]) a-C atoms, respectively.…”