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. 2010 Mar 17;132(10):3523-32.
doi: 10.1021/ja909459h.

Synthetic and mechanistic studies on Pd(0)-catalyzed diamination of conjugated dienes

Baoguo Zhao  1 , Haifeng Du, Sunliang Cui, Yian Shi
Affiliations

Synthetic and mechanistic studies on Pd(0)-catalyzed diamination of conjugated dienes

Baoguo Zhao et al. J Am Chem Soc. .

Abstract

Various dienes and a triene can be regioselectively diaminated at the internal double bond with good yields and high diastereoselectivity using di-tert-butyldiaziridinone (5) as the nitrogen source and Pd(PPh(3))(4) (1-10 mol %) as the catalyst. Kinetic studies with (1)H NMR spectroscopy show that the diamination is first-order in total Pd catalyst and inverse first-order in PPh(3). For reactive dienes, such as 1-methoxybutadiene (6g) and alkyl 1,3-butadienes (6a, 6j), the diamination is first-order in di-tert-butyldiaziridinone (5) and zero-order in the olefin. For olefins with relatively low reactivity, such as (E)-1-phenylbutadiene (6b) and (3E,5E)-1,3,5-decatriene (6i), similar diamination rates were observed when 3.5 equiv of olefins were used. Pd(PPh(3))(2) is likely to be the active species for the insertion of Pd(0) into the N-N bond of di-tert-butyldiaziridinone (5) to form a four-membered Pd(II) complex (A), which can be detected by NMR spectroscopy. The olefin complex (B), formed from intermediate A via ligand exchange between the olefin substrate and the PPh(3), undergoes migratory insertion and reductive elimination to give the diamination product and regenerate the Pd(0) catalyst.

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Figures

Figure 1
Figure 1
Monitoring of the reaction of Pd(PPh3)4 with di-tert-butyldiaziridinone (5) and the subsequent diamination of (E)-1-phenylbutadiene (6b) by 1H NMR spectroscopy. Pd(PPh3)4 (0.030 mmol) reacted with di-tert-butyldiaziridinone (5) (0.020 mmol) in dry benzene-d6 (0.6 mL) in an NMR tube under argon atmosphere at 40 °C for 85 min, followed by the addition of (E)-1-phenylbutadiene (6b) (0.040 mmol). The NMR spectra were recorded at 40 °C.
Figure 2
Figure 2
Monitoring of the reaction of Pd(PPh3)4 with di-tert-butyldiaziridinone (5) and the subsequent diamination of (E)-1-methoxybutadiene (6g) by 1H NMR spectroscopy. Pd(PPh3)4 (0.030 mmol) reacted with di-tert-butyldiaziridinone (5) (0.02 mmol) in dry benzene-d6 (0.6 mL) in an NMR tube under argon atmosphere at 40 °C for 85 min, followed by the addition of (E)-1-methoxybutadiene (6g) (E:Z = 15.7:1, E isomer: 0.040 mmol). The NMR spectra were recorded at 40 °C.
Figure 3
Figure 3
Monitoring of the reaction between di-tert-butyldiaziridinone (5) (0.030 mmol) and Pd(PPh3)4 (0.030 mmol) by 31P NMR spectroscopy. The reaction was carried out at 40 °C, and 31P NMR spectra were collected at room temperature (for higher quality spectra). “reaction mixture + PPh3”: additional PPh3 (0.040 mmol) was added to the reaction mixture after 85 min. “reaction mixture + Pd(PPh3)4”: additional Pd(PPh3)4 (0.010 mmol) was added to the reaction mixture after 85 min in a separate experiment.
Figure 4
Figure 4
Plots of concentrations of di-tert-butyldiaziridinone (5), diamination product (7g), and their sum (5+7g) against the reaction time (min) for the diamination of 1-methoxybutadiene (6g) (E:Z = 15.7:1, E isomer: 0.24 mmol) with 5 (0.20 mmol) and Pd(PPh3)4 (0.020 mmol) in dry benzene-d6 (1.2 mL) at 40 °C in an NMR tube.
Figure 5
Figure 5
Plot of ln([5]0/[5]) against the reaction time for the diamination of 1-methoxybutadiene (6g) (E:Z = 15.7:1, E isomer: 0.24 mmol) with 5 (0.20 mmol) and Pd(PPh3)4 (0.020 mmol) in dry benzene-d6 (1.2 mL) in an NMR tube at 40 °C. [5]0 stands for the initial concentration of 5 in M and [5] stands for the concentration of 5 in M at a particular reaction time.
Figure 6
Figure 6
Plots of the conversion of di-tert-butyldiaziridinone (5) against the reaction time (min) for the diamination of 1-methoxybutadiene (6g) with different initial olefin concentrations. The diaminations were carried out with 6g (E:Z = 15.7:1, E isomer: 0.12 mmol, 0.24 mmol, 0.47 mmol, 0.62 mmol, 0.94 mmol, or 1.25 mmol), di-tert-butyldiaziridinone (5) (0.40 mmol), and Pd(PPh3)4 (0.040 mmol) in dry benzene-d6 (1.2 mL) in an NMR tube at 40 °C.
Figure 7
Figure 7
The plot of 1/kobs against the concentration of free PPh3 for the diamination of 1-methoxybutadiene (6g) (E:Z = 15.7:1, E isomer: 0.12 mmol) with di-tert-butyldiaziridinone (5) (0.10 mmol), Pd(PPh3)4 (0.010 mmol), and added PPh3 (0, 0.010, 0.030, 0.070, and 0.10 mmol, respectively) in dry benzene-d6 (1.2 mL) in an NMR tube at 40 °C. The value of [PPh3]free is corresponding to [PPh3]added + [Pd(PPh3)4]0.
Figure 8
Figure 8
The plot of kobs against [Pd(PPh3)4]0 for the diamination of 1-methoxybutadiene (6g) (E:Z = 15.7:1, E isomer: 0.12 mmol) with di-tert-butyldiaziridinone (5) (0.10 mmol), various amounts of Pd(PPh3)4 (0.010–0.030 mmol), and fixed amount of free PPh3 (0.040 mmol) in dry benzene-d6 (1.2 mL) in an NMR tube at 40 °C. Additional PPh3 (0.030–0.010 mmol) was added to maintain the amount of PPh3 (0.040 mmol) in each reaction [PPh3 (added) = 0.040 mmol – Pd(PPh3)4 (added)].
Figure 9
Figure 9
Plots of [7] against the reaction time for the diaminations of different dienes or triene with di-tert-butyldiaziridinone (5) (0.20 mmol), Pd(PPh3)4 (0.020 mmol) in dry benzene-d6 (1.2 mL) in an NMR tube at 40 °C. For 1-methoxybutadiene (6g): E:Z = 15.7:1, E isomer: 0.24 mmol; for (E)-1,3-decadiene (6a): 0.24 mmol; for (3E,5E)-undeca-1,3,5-triene (6i): 3.5 equiv (0.70 mmol), 1.2 equiv (0.24 mmol); for methyl 1,3-butadiene-1-carboxylate (6h): E:Z = 8.3:1, E isomer: 0.24 mmol.
Figure 10
Figure 10
Plots of [7] against the reaction time for the reactions betwen Pd(II) intermediate A and different dienes or triene (6) (E isomer: 0.040 mmol) in dry benzene-d6 (0.6 mL) at 40 °C in an NMR tube. For 1-methoxybutadiene (6g): E:Z = 15.7:1, E isomer: 0.040 mmol; for (E)-1,3-pentadiene (6j): 0.040 mmol; for (E)-1,3-decadiene (6a): 0.040 mmol; for (E)-1-phenylbutadiene (6b): 0.040 mmol; for (3E,5E)-undeca-1,3,5-triene (6i): 0.040 mmol; for methyl 1,3-butadiene-1-carboxylate (6h): E:Z = 8.3:1, E isomer: 0.040 mmol. Compound A was prepared by reacting di-tert-butyldiaziridinone (5) (0.020 mmol) with Pd(PPh3)4 (0.030 mmol) in dry benzene-d6 (0.6 mL) at 40 °C in an NMR tube for 85 min.
Figure 11
Figure 11
Plots of 1/[A] against [6i]/[5] for the diaminations of (3E,5E)-undeca-1,3,5-triene (6i) (0.20 mmol) with di-tert-butyldiaziridinone (5) (0.10 mmol), Pd(PPh3)4 (0.020 mmol), and different amounts of PPh3 added (0 mmol; 0.020 mmol; 0.050 mmol) in dry benzene-d6 (1.2 mL) at 40 °C in an NMR tube.
Scheme 1
Scheme 1
Scheme 2
Scheme 2
Scheme 3
Scheme 3
Scheme 4
Scheme 4
Scheme 5
Scheme 5
Scheme 6
Scheme 6
Scheme 7
Scheme 7
Scheme 8
Scheme 8
Proposed catalytic cycle for Pd(0)-catalyzed diamination of olefin.
Scheme 9
Scheme 9
Scheme 10
Scheme 10
Scheme 11
Scheme 11
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