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Ministry of Education, Culture, Sports, Science, and
Technology, Japan.
Supplementary data
Supplementary data associated with this article can be
9. For reviews on transition metal catalysis using phosphine
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References and notes
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13. Asymmetric allylic alkylation of 2a with dimethyl malon-
ate in the presence of other hexafluorophosphate salts
gave less satisfactory results. NaPF6: 24 h, 29%, 3a/
3a0 = 97/3, 75% ee (Table 1, entry 1), LiPF6: 24 h, 76%,
3a/3a0 = 82/18, 81% ee, KPF6: 24 h, 6%, 3a/3a0 = 97/3,
23% ee, AgPF6: 24 h, 42%, 3a/3a0 = 97/3, 45% ee. These
results indicate that the counter cation of hexafluorophos-
phate salt might also play an important role in the present
asymmetric catalysis.
14. General procedure for the Ir-catalyzed asymmetric allylic
alkylation (Table 3, entry 1): To a stirred mixture of
[Ir(cod)Cl]2 (3.46 mg, 0.00515 mmol), (S,RP)-1i (4.82 mg,
0.0103 mmol), NaPF6 (3.46 mg, 0.0206 mmol), LiOAc
(1.40 mg, 0.0206 mmol), and 2a (39.6 mg, 0.206 mmol) in
CH2Cl2 (0.82 mL) at room temperature was added BSA
(147 lL, 0.618 mmol), and the solution was stirred for
5 min at the same temperature. Dimethyl malonate (70 lL,
0.618 mmol) was added and the resulting mixture was
stirred for 24 h. The reaction mixture was concentrated
under reduced pressure, and the obtained residue was
purified by flash column chromatography (SiO2, hexane/
ethyl acetate: 20/1) to give (S)-3a as colorless oil (47.5 mg,
93%, 90% ee, 3a/3a0 = 99/1).
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