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. Author manuscript; available in PMC: 2020 Nov 2.
Published in final edited form as: J Am Chem Soc. 2020 Jul 1;142(28):12394–12399. doi: 10.1021/jacs.0c04725

Table 2.

Rhodium-Catalyzed Enantioselective Si–H Bond Insertion of Diphenyl Diazomethanes D13–D30

graphic file with name nihms-1637472-t0007.jpg
entrya R1 R2 Δσp (R1-R2)b product yield(%) ee(%)
1 NO2 NMe2 1.38 P13 66 96
2 NO2 OMe 1.05 P14 78 99
3 NO2 Me 0.95 P15 87 99
4 NO2 F 0.72 P16 86 98
5 NO2 Br 0.55 P17 80 95
6 NO2 CI 0.5 P18 88 96
7 NO2 CF3 0.24 P19 58 86
8 CN CF3 0.12 P20 42 36
9 CF3 OMe 0.81 P21 78 98
10c CF3 Me 0.71 P22 85 94(S)
11c CF3 F 0.48 P23 63 92
12c CF3 Br 0.31 P24 71 67
13c CF3 CI 0.26 P25 73 76(R)
14 OCF3 OMe 0.62 P26 58 93
15 Br OMe 0.50 P27 58 94
16 CI OMe 0.55 P28 59 93
17c F OMe 0.33 P29 43 77(R)
18 Me OMe 0.10 P30 40 56
graphic file with name nihms-1637472-t0008.jpg
a

Reaction conditions: hydrazone (0.2 mmol), MnO2 (3.5 equiv), MgSO4, DCM, rt, 5–6 h; then PhMe2SiH (1.2 equiv), C2 (0.1 mol %), DCM, 0 °C. Isolated yields were given. The ee values were determined by chiral HPLC analysis.

b

The Hammett substituent constant difference for para substituents.

c

The ee value was determined by the corresponding alcohol obtained through the oxidation of Si–H insertion product. A plot of log(er) vs Δσp (R1-R2) is shown in Figure S2.