57116-96-8Relevant articles and documents
Access to Unsymmetrically Substituted Diaryl Gold N-Acyclic Carbene (NAC) and N-Heterocyclic Carbene (NHC) Complexes via the Isonitrile Route
Vethacke, Vanessa,Claus, Vanessa,Dietl, Martin C.,Ehjeij, Daniel,Meister, Arne,Huber, Jonas F.,Paschai Darian, Leon K.,Rudolph, Matthias,Rominger, Frank,Hashmi, A. Stephen K.
, p. 536 - 554 (2021/10/20)
A variety of unsymmetric diaryl gold N-acyclic carbene (NAC) complexes was synthesized via the isonitrile route by three different methods: (a) solvent free in a melt, (b) mechanochemically and (c) in THF at room temperature. The latter method can also be used to synthesize unsaturated gold NHC complexes. These methods overall offer access to a broad array of new complexes and remove one of the previous limitations of the isonitrile route to NAC and NHC complexes of gold, namely the inability to react with the less nucleophilic aromatic amines. The new complexes also proved to be successful as pre-catalysts in the gold-catalyzed phenol synthesis. (Figure presented.).
Heterocyclopentanediyls vs heterocyclopentadienes: A question of silyl group migration
Beer, Henrik,Bresien, Jonas,Michalik, Dirk,R?lke, Anne-Kristin,Schulz, Axel,Villinger, Alexander,Wustrack, Ronald
, p. 14435 - 14445 (2020/12/29)
The reaction of the singlet biradical [P(μ-NHyp)]2 (Hyp = hypersilyl, (Me3Si)3Si) with different isonitriles afforded a series of five-membered N2P2C heterocycles. Depending on the steric bulk of the substituent at the isonitrile, migration of a Hyp group was observed, resulting in two structurally similar but electronically very different isomers. As evidenced by comprehensive spectroscopic and theoretical studies, the heterocyclopentadiene isomer may be regarded as a rather unreactive closed-shell singlet species with one localized N=P and one C=P double bond, whereas the heterocyclopentanediyl isomer represents an open-shell singlet biradical with interesting photochemical properties, such as photoisomerization under irradiation with red light to a [2.1.0]- housane-type species.
Palladium-Catalyzed Diarylation of Isocyanides with Tetraarylleads for the Selective Synthesis of Imines and α-Diimines
Tran, Cong Chi,Kawaguchi, Shin-Ichi,Kobiki, Yohsuke,Matsubara, Hitomi,Tran, Dat Phuc,Kodama, Shintaro,Nomoto, Akihiro,Ogawa, Akiya
, p. 11741 - 11751 (2019/10/02)
Using tetraaryllead compounds (PbAr4) as arylating reagents, isocyanides undergo selective diarylation in the presence of palladium catalysts such as Pd(OAc)2 or Pd(PPh3)4 to afford imines and/or α-diimines based on the isocyanide employed. With aliphatic isocyanides, imines are obtained preferentially, whereas α-diimines are formed in the case of electron-rich aromatic isocyanides. The differences in imine/α-diimine selectivity can be attributed to the stability of imidoylpalladium intermediates formed in this catalytic reaction. Compared with other arylating reagents, tetraaryllead compounds are excellent candidates for use in the selective transformations to imines and/or α-diimines, especially in terms of inhibiting the oligomerization of isocyanides, which results in a lower product selectivity in many transition-metal-catalyzed reactions of isocyanides.