Reaction of a stable aminoarylcarbene with 2-chloroacrylonitrile: dearomatizing cyclization rather than cyclopropanation

The reaction of a stable aminoarylcarbene with 2-chloroacrylonitrile is reported. The resulting 1/1 adduct has been spectroscopically and structurally characterized. The initial Michael addition is not followed by cyclopropane formation but by a dearomatizing cyclization affording an original bicyclic structure.     

Studies on the 4-benzoylpyridine-3-carboxamide entity as a fragment model of the Isoniazid-NAD adduct

An ortho-metallation-electrophilic substitution sequence was employed as a key step to build the 4-benzoylpyridine framework. It was found that 4-benzoylpyridine-3-carboxamide and an N-pyridyl alkylated derivative both exist in a unique cyclized hemiamidal structure, not in the usually expected keto-amide open form. These structures represent fragment models of the Isoniazid-NAD adducts involved in the mechanism of action of the antituberculous drug Isoniazid.     

Formation of the monoanion [Ar*P(BH3)(mu-BH2)2H]- with a symmetrically bridging hydride from the attempted synthesis of the dianion [Ar*P(BH3)3]2-

Addition of an excess of BunLi to the bis(borano)phosphide complex [Ar*PH(BH3)2]-Li+ 1 (Ar* = 2,4,6-tri-tert-butylphenyl) and subsequent treatment with BH3, gives the anionic complex [Ar*P(BH3)(mu-BH2)2H]-Li+ 2 instead of the expected tris(borano)phosphide dilithium, [Ar*P(BH3)3]2-2Li+ 3.     

Amino-aryl-carbenes: alternative ligands for transition metals?

Despite the presence of a single amino substituent, an amino-anthryl-carbene was found to behave as a strong sigma-donor weak pi-acceptor ligand toward rhodium(I) fragments.     

A stable distannirane

The first three-membered ring compound containing two tin and one carbon atoms, 1,1,2,2-tetra(2,4,6-triisopropylphenyl)-3-fluorenylidene-1,2-distannirane, has been synthesized in a two-step procedure from the 9-[bis(2,4,6-triisopropylphenyl)fluorostannyl]chloromethylenefluorene.     

The use of a germene for the synthesis of esters of alpha-germyl-substituted alpha-amino acid and alpha-aminophosphonic acid

The first alpha-germyl-substituted alpha-amino ester and alpha-germyl-substituted alpha-aminophosphonic ester have been synthesized by a one-pot reaction between the germene Mes2Ge=CR2 (CR2 = fluorenylidene) and the iminoester or iminophosphonate Ph(H)C=NCH2-Y (Y = COOMe, P(O)(OEt)2).