Tungsten Compounds with CO or Isocyanides

Baker, Murray V.; Brown, David M.

doi:10.1016/b0-08-045047-4/00073-x

Cited by 1 publication

(1 citation statement)

References 1,241 publications

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“…With regard to the mechanism, the experimental data and literature information point toward the catalytic cycle shown in Scheme . Initially, W(CO) 6 readily dissociates two CO ligands upon irradiation with 365 nm light, followed by coordination with PPh 3 to afford the trans - W complex. Then, trans - W was activated under light irradiation to afford trans - W * (please see UV spectrum of trans - W in Figure S8).…”

Section: Resultsmentioning

confidence: 99%

Light-Promoted Low-Valent-Tungsten-Catalyzed Ambient Temperature Amination of Boronic Acids with Nitroaromatics

et al. 2022

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Triggering C−N bond formation with nitroaromatics and boronic acids at mild conditions is highly desirable, since most prior works were carried out under harsh conditions and sometimes suffered from poor chemo-or regioselectivity. Herein, a low-valent-tungsten-catalyzed reaction that enables the ambient temperature amination of boronic acids with nitroaromatics is disclosed. With readily available W(CO) 6 as a precatalyst under external-photosensitizer-free conditions, nitroaromatics smoothly undergo C−N coupling reactions with their boronic acid partners, delivering structurally diverse secondary amines in good yields (>50 examples, yields up to 96%). This methodology is both scalable and highly chemoselective and engages both aliphatic and aromatic boronic acid partners. The catalysis is initiated by the deoxygenation of nitroaromatics by a trans-[W(CO) 4 (PPh 3 ) 2 ] (trans-W, PPh 3 = triphenylphosphine) complex, which forms in situ via ligand replacement.

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Section: Resultsmentioning

confidence: 99%