Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 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.

PubMed Disclaimer

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
See this image and copyright information in PMC

Similar articles

See all similar articles

Cited by

See all "Cited by" articles

References

    1. For leading reviews, see: Lucet D, Gall TL, Mioskowski C. Angew. Chem., Int. Ed. 1998;37:2580.. Mortensen MS, O'Doherty GA. Chemtracts: Org. Chem. 2005;18:555.. Kotti SRSS, Timmons C, Li G. Chem. Biol. Drug Des. 2006;67:101.. Kizirian J-C. Chem. Rev. 2008;108:140.. Lin G-Q, Xu M-H, Zhong Y-W, Sun X-W. Acc. Chem. Res. 2008;41:831.. de Figueiredo RM. Angew. Chem., Int. Ed. 2009;48:1190.. Cardona F, Goti A. Nat. Chem. 2009;1:269..

    1. For leading references on recent Ritter-type diamination see: Li G, Kim SH, Wei H-X. Tetrahedron Lett. 2000;41:8699.. Booker-Milburn KI, Guly DJ, Cox B, Procopiou PA. Org. Lett. 2003;5:3313..

    1. For examples of metal-mediated diaminations, see: Tl: Aranda VG, Barluenga J, Aznar F. Synthesis. 1974:504.. Os: Chong AO, Oshima K, Sharpless KB. J. Am. Chem. Soc. 1977;99:3420.. Muñiz K. Eur. J. Org. Chem. 2004:2243.. Hg: Barluenga J, Alonso-Cires L, Asensio G. Synthesis. 1979:962.. Co: Becker PN, White MA, Bergman RG. J. Am. Chem. Soc. 1980;102:5676.. Mn: Fristad WE, Brandvold TA, Peterson JR, Thompson SR. J. Org. Chem. 1985;50:3647..

    1. For recent Cu(II)-mediated intramolecular diamination, see: Zabawa TP, Kasi D, Chemler SR. J. Am. Chem. Soc. 2005;127:11250.. Zabawa TP, Chemler SR. Org. Lett. 2007;9:2035..

    1. For Rh(II), Cu(I), and Fe(III)-catalyzed diamination with TsNCl2 or TsNBr2, see: Li G, Wei H-X, Kim SH, Carducci MD. Angew. Chem., Int. Ed. 2001;40:4277.. Wei H-X, Kim SH, Li G. J. Org. Chem. 2002;67:4777.. Han J, Li T, Pan Y, Kattuboina A, Li G. Chem. Biol. Drug. Des. 2008;71:71..

Publication types