Alkali metal and stoichiometric effects in intermolecular hydroamination catalysed by lithium, sodium and potassium magnesiates

Abstract

Cooperative catalytic hydroamination of diphenylacetylene and styrene is accomplished by magnesiates with efficiency dependent on the alkali metal and monoanionic or dianionic nature of the ate with dianionic [(PMDETA)2K2Mg(CH2SiMe3)4] performing best.

Alkali‐Metal Mediation: Diversity of Applications in Main‐Group Organometallic Chemistry

“…Alkali metals do not only cooperate with each other, they show synergistic effects with metals from essentially the entire periodic table. For example, in 2019 Hevia and co‐workers reported a catalytic intermolecular hydroamination mediated by alkali‐metal magnesiates of the general forms (AM)MgR 3 and (AM) 2 MgR 4 (AM=Li, Na, K; R=CH 2 SiMe 3 ) [4a] . Note that these complexes are referred to as lower order and higher order magnesiates, respectively, reflecting the relative stoichiometry of the R substituent.…”

Ambient Moisture Accelerates Hydroamination Reactions of Vinylarenes with Alkali‐Metal Amides under Air

“…(Scheme ) . Since establishing efficient main‐group bimetallic catalysts for hydroamination reactions, we have become interested in developing s‐block organometallic approaches that are operationally simple for this atom‐efficient transformation dedicated to practical everyday laboratory use. Lithium amides are simple to synthesize and simple to use reactants for such reactions .…”

Untangling the Complexity of Mixed Lithium/Magnesium Alkyl/Alkoxy Combinations Utilised in Bromine/Magnesium Exchange Reactions

“…and 3 a, respectively]. Considering the alkyl-rich constitution of higher order magnesiate 7, [16] coupled with its ability to quantitatively promote Br/Mg exchange of 1 a, the selective formation of 2 a when 1 a was reacted with the LiOR/sBu 2 Mg combination became even more puzzling. In an attempt to mimic the reaction conditions when using this mixed alkyl/ alkoxide reagent, one molar equivalent of Mg(OR) 2 (which is the other product observed from disproportionation of 6 into 7) was introduced to a suspension of 9 in toluene which led to the quantitative formation of 2 a (Figure 4).…”