Angewandte Chemie International Edition
10.1002/anie.201805680
COMMUNICATION
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Scheme 5. Mechanistic Considerations. [1] Isolated yields. [2] GC-FID yields.
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The kinetic profile revealed a slightly higher e.r. in the initial
phase of the reaction (97:3) until 4 hours reaction time when it
was found to remain constant (95.5:4.5) (see SI). No non-linear-
effect was observed for this transformation (see SI). Additionally,
the ratio of rhodium to ligand has an almost linear correlation to
the yield of 2a, while the enantiomeric ratio is completely
independent, even when an excess of rhodium is used (eq. B),
which suggests, that only one phosphonite ligand is coordinating
to the rhodium center in the catalytically active species. A
competition experiment between the electron-rich 4-iodoanisole
and the electron-poor 1-chloro-4-iodobenzene in the initial phase
of the reaction showed significant more product of the electron-
rich aryl iodide 2j (21% compared to 12% of 2h). Further, the rates
of separate reactions in the initial phase is significantly higher if 4-
iodoanisole is applied (see SI), which suggests that the oxidative
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determining step in this transformation (eq. C).
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on
a rhodium(I) precatalyst and a simple Taddol-derived
1
phosphonite ligand, which was used for the first intermolecular
enantioselective Csp3–H activation by rhodium. α-N-arylated
tetrahydroquinolines and piperazine were prepared in an
enantioselective fashion for the first time. This methodology was
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5
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We thank the Deutsche Forschungsgemeinschaft (Leibniz Award)
and the Fonds der Chemischen Industrie (F.K.) for generous
financial support. We also thank Dr. Klaus Bergander for NMR
assistance, Mirxan Farizyan for synthetic efforts and Tobias
Knecht for helpful discussions.
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[
Keywords: arylation • C−H activation • enantioselective •
heterocycle • rhodium
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