A bisoxazoline-derived NHC known as IBiox-6 reacted smoothly with Ni[P(OEt) 3 ] 2 Br 2 and Ni(PPh 3 ) 2 Br 2 to give the respective heteroleptic Ni(II) complexes Ni(IBiox-6)[P(OEt) 3 ]Br 2 (1) and Ni(IBiox-6)(PPh 3 )Br 2 (2) in yields of 60% and 71%. Their crystal structures were characterized to reveal a rare cis disposition of the IBiox-6 ligand to the phosphite ligand in 1, while 2 possessed the more common trans configuration. Both complexes catalyzed the cross-electrophile coupling of benzyl chlorides with aryl chlorides and fluorides in the presence of Mg turnings at 50 °C via a "real one-pot" procedure, featuring no requirement for temperature variation or portionwise addition of any coupling partner. In particular, complex 1 showed a better balance between the catalytic activity and selectivity. The scope of the procedure catalyzed by 1 and Mg turnings was investigated, providing a highly selective, simple, and practical approach to the synthesis of diarylmethanes with high steric hindrance and various functional groups, including oligo-diarylmethane with asymmetric structures.
A tandem isomerization/anti-Markovnikov hydroarylation of unactivated internal alkenes with several types of heteroarene, including benzimidazoles, indoles, benzofurans, and furans, was realized for the first time by using a catalytic system...
We herein describe an accessible ligand-controlled nickel-catalyzed
tandem isomerization/regiodivergent hydroheteroarylation of α-alkenes
with a series of heteroarenes, wherein the NHC ligand of heteroleptic
Ni(II) complexes of the type Ni(NHC)[P(OEt)3]Br2 displayed significant effects on regulation. In the presence of
NaO
t
Bu, Ni(IMes)[P(OEt)3]Br2 enables CC bond isomerization of α-alkenes
over up to four sp3 carbon atoms to afford branched products,
while Ni(IPr*OMe)[P(OEt)3]Br2 greatly
deactivates α-alkene isomerization and favors the formation
of linear products.
Rare earth/lithium complexes stabilized by ethylenediamine-bridged bis(phenolate) ligands have been synthesized and characterized. In addition to five rare earth/lithium amides isolated as major complexes, two other rare earth/lithium complexes bearing...
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