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PreprintCC BYChemRxiv

Hydrosilane-Dependent Regiodivergence for Rhodium-Catalyzed Dearomative Hydrosilylation of Quinolines

  • Mei Shu1,2,3,4
  • Sehoon Park3,4,5
5 affiliations
  1. 1Department of Chemistry, and Guangdong Provincial Key Laboratory of Catalysis
  2. 2Southern University of Science and Technology
  3. 3Department of Chemistry
  4. 4Guangdong-Technion Israel Institute of Technology
  5. 5Technion-Israel Institute of Technology
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Abstract

Regiodivergent dearomative hydroelementation (E = Si, B) of quinolines represent a powerful, atomeconomic strategy for the synthesis of biologically valuable 1,2- and 1,4-dihydroquinolines (DHQ) scaffolds. However, achieving such regiodivergent H[E] additions at the C2 and C4 positions within a unified catalytic system remains highly challenging. Herein, we report a simple [Rh(cod)Cl]2/PPh3 catalytic system that enables regioselective hydride incorporation dictated solely by the choice of hydrosilane (Ph2SiH2 vs. Me2RSiH, R = Et or Ph). While the Ph2SiH2-mediated 1,2-hydrosilylation protocol proceeds efficiently at 23 oC, the 1,4-hydrosilylation with Me2EtSiH requires a prolonged reaction time or an elevated temperature (23 to 50 oC) to achieve high yields. Preliminary mechanistic studies under the Ph2SiH2 vs. Me2PhSiH systems indicate that (i) chloro-free, phosphine-ligated Rh hydride species in situ generated during the initiation stage serves as the key resting species; (ii) a classic Chalk–Harrod sequence operates to yield the 1,2-DHQ irrespective of the hydrosilane used; (iii) the Me2PhSiH system promotes a facile isomerization of the kinetic 1,2-DHQ product to the 1,4-DHQ via an exclusive 3,4-hydrorhodation process; and (iv) the dearomative 1,2-hydrorhodation is reversible under the Ph2SiH2 system and the liberated 1,2-DHQ is completely resistant to subsequent isomerization.

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Cite

BibTeXRIS
BibTeX
@misc{shu2026hydrosilanedependent,
  title = {{Hydrosilane-Dependent Regiodivergence for Rhodium-Catalyzed Dearomative Hydrosilylation of Quinolines}},
  author = {Mei Shu and Sehoon Park},
  howpublished = {ChemRxiv},
  year = {2026},
  month = oct,
  doi = {10.26434/chemrxiv.15010954/v1},
  url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010954/v1},
  note = {CC BY},
}
RIS
TY  - UNPB
TI  - Hydrosilane-Dependent Regiodivergence for Rhodium-Catalyzed Dearomative Hydrosilylation of Quinolines
AU  - Mei Shu
AU  - Sehoon Park
PY  - 2026
DA  - 2026/10/23
PB  - ChemRxiv
DO  - 10.26434/chemrxiv.15010954/v1
UR  - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010954/v1
AB  - Regiodivergent dearomative hydroelementation (E = Si, B) of quinolines represent a powerful, atomeconomic strategy for the synthesis of biologically valuable 1,2- and 1,4-dihydroquinolines (DHQ) scaffolds. However, achieving such regiodivergent H[E] additions at the C2 and C4 positions within a unified catalytic system remains highly challenging. Herein, we report a simple [Rh(cod)Cl]2/PPh3 catalytic system that enables regioselective hydride incorporation dictated solely by the choice of hydrosilane (Ph2SiH2 vs. Me2RSiH, R = Et or Ph). While the Ph2SiH2-mediated 1,2-hydrosilylation protocol proceeds efficiently at 23 oC, the 1,4-hydrosilylation with Me2EtSiH requires a prolonged reaction time or an elevated temperature (23 to 50 oC) to achieve high yields. Preliminary mechanistic studies under the Ph2SiH2 vs. Me2PhSiH systems indicate that (i) chloro-free, phosphine-ligated Rh hydride species in situ generated during the initiation stage serves as the key resting species; (ii) a classic Chalk–Harrod sequence operates to yield the 1,2-DHQ irrespective of the hydrosilane used; (iii) the Me2PhSiH system promotes a facile isomerization of the kinetic 1,2-DHQ product to the 1,4-DHQ via an exclusive 3,4-hydrorhodation process; and (iv) the dearomative 1,2-hydrorhodation is reversible under the Ph2SiH2 system and the liberated 1,2-DHQ is completely resistant to subsequent isomerization.
ER  -