Journal
ACS CATALYSIS
Volume 6, Issue 6, Pages 3496-3505Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acscatal.6b00572
Keywords
denitrogenative annulations; density functional theory; heterocycles; axially chiral isoquinolones; nickel
Categories
Funding
- 100-Talent Program in Shanxi Province
- Taiyuan University of Science and Technology of China
- National Natural Science Foundation of China [215722096, 21302088]
- National Key Basic Research Program of China (973 Program) [2013CB834802]
- Shenzhen Overseas High Level Talents Innovation Plan of Technical Innovation Project [KQCX20150331101823702]
- Shenzhen Special Funds for the Development of Biomedicine, Internet, New Energy, and New Material Industries [JCYJ20150430160022517]
- South University of Science and Technology of China [FRG-SUSTC1501A-16]
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The mechanism of Ni(0)-catalyzed denitrogenative transannulation of 1,2,3-benzotriazin-4(3H)-ones with alkynes to access isoquinolones has been comprehensively studied by a density functional theory (DFT) calculation and control experimental investigation. The results indicate that the transformations proceed via a sequential nitrogen extrusion, carbometalation, Ni C bond insertion, and reductive elimination process. A frontier molecular orbital (FMO) theory and natural bond orbital (NBO) analysis reveals that the advantages of substituents on chemical reactivity and regioselectivity exist for multiple reasons: (1) Phenyl groups on the N atom of benzotriazinone and/or unsymmetrical alkynes mainly account for the high reactivity and regioselectivity via its electronic effect. (2) The pi center dot center dot center dot pi-interaction between the phenyl substituent on the alkyne and triazole ring might partially contribute to the high regioselectivity when unsymmetrical alkynes were employed as the substrates. Furthermore, DFT calculations successfully explain the origin of enantioselectivity and discrepancy of reactivities between different N-substituted benzotriazinones for the asymmetric construction of axially chiral isoquinolones in an atroposelective manner. The calculated results indicate that high enantioselectivity is mainly determined by the structural difference between these two transition states of the key annulation step, which lies in the orientation of the naphthyl substituent relative to the chiral ligand.
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