Details

Autor(en) / Beteiligte

• Hao, Han
• Manßen, Manfred
• Schafer, Laurel L

Titel

Tantalum ureate complexes for photocatalytic hydroaminoalkylation

Ist Teil von

• Chemical science (Cambridge), 2023-05, Vol.14 (18), p.4928-4934

Ort / Verlag

England: Royal Society of Chemistry

Erscheinungsjahr

2023

Quelle

Free E-Journal (出版社公開部分のみ）

Beschreibungen/Notizen

• Using a tantalum ureate pre-catalyst, photocatalytic hydroaminoalkylation of unactivated alkenes with unprotected amines at room temperature is demonstrated. The combination of Ta(CH 2 SiMe 3 ) 3 Cl 2 and a ureate ligand with a saturated cyclic backbone resulted in this unique reactivity. Preliminary investigations of the reaction mechanism suggest that both the thermal and photocatalytic hydroaminoalkylation reactions begin with N-H bond activation and subsequent metallaaziridine formation. However, a select tantalum ureate complex, through ligand to metal charge transfer (LMCT), results in photocatalyzed homolytic metal-carbon bond cleavage and subsequent addition to unactivated alkene to afford the desired carbon-carbon bond formation. Origins of ligand effects on promoting homolytic metal-carbon bond cleavage are explored computationally to support enhanced ligand design efforts. Using a tantalum ureate pre-catalyst, photocatalytic hydroaminoalkylation of unactivated alkenes with unprotected amines at room temperature is demonstrated.