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. 2022 Oct 6;13(42):12433–12439. doi: 10.1039/d2sc05210e

Screening conditions for regiodivergent tandem reactiona.

graphic file with name d2sc05210e-u3.jpg
Entry [Pd] L Acid x Yieldb (%) rrc
1 Pd(PPh3)4 A1 20 75 52 : 48
2 Pd(PPh3)4 A2 20 65 63 : 37
3 Pd(PPh3)4 A3 20 60 54 : 46
4 Pd(PPh3)4 A1 50 90 75 : 25
5 Pd(PPh3)4 A1 100 91 94 : 6
6 Pd(OAc)2 PPh3 A1 20 48 60 : 40
7 [Pd(allyl)Cl]2 PPh3 A1 20 36 67 : 33
8 Pd(allyl)Cp PPh3 A1 20 71 13 : 87
9 Pd(allyl)Cp PPh3 A2 20 80 40 : 60
10 Pd(allyl)Cp PPh3 A3 20 82 8 : 92
11 Pd(allyl)Cp PPh3 A4 20 47 24 : 76
12 Pd(allyl)Cp PPh3 A5 20 Trace
13 Pd(allyl)Cp PPh3 A3 100 62 44 : 56
14d Pd(PPh3)4 A1 100 87 96 : 4
15d Pd(allyl)Cp PPh3 A3 20 73 30 : 70
16e Pd(PPh3)4 A2 40 80 95 : 5
a

Unless noted otherwise, reactions were performed with 1,6-enyne 5b (0.1 mmol), imine 3a (0.05 mmol), [Pd] source (10 mol%), L (20 mol%), acid (x mol%) and 4 Å MS (20 mg) in degassed dry toluene (0.5 mL) at 70 °C for 12 h under Ar.

b

Isolated yield.

c

rr = 7a : 8a, determined by 1H-NMR analysis.

d

With 5c (0.1 mmol) instead of 5b.

e

With 1b (0.1 mmol) and 2a (0.1 mmol) instead of 5b at 80 °C.