The direct use of ammonia in transition-metal promoted C−H bond amination for the synthesis of primary amines is considered to be one of the major challenges in synthetic organic chemistry. Herein, we report that such transformation can be successfully achieved via nickel-promoted amination of inert arene C−H bonds with ammonia gas assisted by an 8-amino-quinoline directing group.
An efficient nickel-promoted selective monocyanation of benzamides with TMSCN via 8-aminoquinoline directed ortho C-H activation has been developed. Varieties of functionalized ortho-cyanated (hetero)aryl nitriles can be selectively synthesized in moderate to good yields. These cyanation products can be easily transformed into various 3-imino-1-oxoisoindolines in a one-pot procedure. The mild reaction conditions, use of cheap and commercially available reagents, wide functional group tolerance, and operational convenience make this protocol practical to the synthetic community.
A highly monoselective synthesis
of ferrocenyl alkynes was achieved
via Cu-promoted ferrocene C(sp2)–H bond activations.
The reaction employs an 8-aminoquinoline group as the directing group
and terminal alkynes as the alkyne source. It was found the alkynylation
products actually complex with the in situ generated Cu(I) ions to
give robust and stable alkyne π-copper complexes. In addition,
these alkyne π-copper complexes could be freed of the copper
ions to give various ferrocenyl alkynes in almost quantitative yields.
The test results also showed that the alkyne π-copper complexes
could be reformed from the free alkynes upon treating them with Cu(I)
salts.
A novel and efficient method for highly regioselective cyanomethylation of 8-aminoquinoline amides at C5 position was developed. Such reactions proceed under transition metalfree and base-free conditions. This protocol features simple operation, high efficiency, good functional group tolerance and broad substrate scope. Moreover, the etherification or acetonation products were also obtained when acetonitrile was replaced by ethers or acetone, and a radical process was involved in the reaction.
A new efficient protocol for the ortho‐methylation of benzamides with DTBP has been developed via Ni(II)‐catalyzed C–H activation directed by 8‐aminoquinoline. This method is performed under base‐free, ligand‐free conditions and utilizes cheap and commercially available reagents. Moreover, the by‐product acetone derived from DTBP does not affect the purification of the product.
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