Ruthenium-Catalyzed Carbocycle-Selective Hydrogenation of Fused Heteroarenes

The homogeneous catalytic hydrogenation of benzo-fused heteroarenes generally provides partially hydrogenated products wherein the heteroaryl ring is preferentially reduced, such as quinoline hydrogenation, leading to 1,2,3,4-tetrahydroquinoline. Herein, we report a carbocycle-selective hydrogenation of fused N-heteroarenes (quinoline, isoquinoline, quinoxaline, etc.) using the Ru complex of a chiral spiroketal-based diphosphine (SKP) as the catalyst, affording the corresponding 5,6,7,8-tetrahydro products in high chemoselectivities. This catalytic system is also effective for the asymmetric carbocycle hydrogenation of fused heteroarenes bearing a boryl or amino group. Experimental studies provided a strong support for the homogeneous nature of the catalysis, and an inner-sphere mechanism was proposed for the hydrogenation. DFT calculations indicated that the hydrogenation is initiated by η4-coordinative activation of quinoline carbocycle to Ru dihydride complex of SKP, followed by metal-to-ligand hydride transfer. Subsequent carbocycle reduction proceeds via consecutive steps of the H2 oxidative addition and C–H reductive elimination.

• Publication year

  2024

• Venue

  Journal of the American Chemical Society

• Publication date

  2024-12-11

• Fields of study

  Medicine, Chemistry

• Identifiers
  DOI 10.1021/jacs.4c05365PMID 39661002PMCID 11673584
• External record

  Open on Semantic Scholar

• Source metadata

  Semantic Scholar, PubMed

• No claims are published for this paper.

• No concepts are published for this paper.

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