117269-62-2Relevant academic research and scientific papers
Preparation of polyfunctional arylmagnesium, arylzinc, and benzylic zinc reagents by using magnesium in the presence of LiCl
Piller, Fabian M.,Metzger, Albrecht,Schade, Matthias A.,Haag, Benjamin A.,Gavryushin, Andrei,Knochel, Paul
supporting information; experimental part, p. 7192 - 7202 (2010/03/05)
The presence of LiCl considerably facilitates the insertion of magnesium into various aromatic and heterocyclic bromides. Several functional groups, such as -OBoc, -OTs, -Cl, -F, -CF3, -OMe, -NMe2, and -N 2NR2, are well tolerated. The presence of a cyano group leads in some cases to competitive reduction of the organic halide to the corresponding ArH compound. The presence of sensitive groups such as methyl or ethyl ester is tolerated upon in situ trapping of the intermediate magnesium reagent with ZnCl2. This method can also be applied to the preparation of functionalized benzylic zinc reagents from benzylic chlorides. In the case of di- or tribromoaryl derivatives, directing groups such as -OPiv, -OTs, -N2NR2, or -OAc orient the zinc insertion (Zn/LiCl) to the ortho-position, while the reaction with Mg/LiCl or Mg/LiCl/ZnCl 2 leads to regioselective insertion into the para-carbon-bromine bond. Large-scale experiments (20-100 mmol) for all of the metalation procedures are described.
Polyfunctional benzylic zinc chlorides by the direct insertion of magnesium into benzylic chlorides in the presence of LiCl and ZnCl2
Metzger, Albrecht,Piller, Fabian M.,Knochel, Paul
supporting information; experimental part, p. 5824 - 5826 (2009/04/13)
Benzylic zinc chlorides bearing various functional groups are smoothly prepared by the direct insertion of magnesium into benzylic chlorides in the presence of LiCl and ZnCl2. The Royal Society of Chemistry.
General Approach to Highly Functionalized Benzylic Organometallics of Zinc and Copper
Berk, Scott C.,Knochel, Paul,Yeh, Ming Chang P.
, p. 5789 - 5791 (2007/10/02)
A general synthesis of highly functionalized benzylic zinc organometallics is described.The corresponding copper derivatives, formed by a transmetalation with CuCN*2LiCl, react in high yields with allylic halides, enones, acyl chlorides, and aldehydes.
