Efficient Palladium-Catalyzed
Amination of Aryl Chlorides Using Dicyclo­hexylamino[(2,6-dimethyl)morpholino]phenylphosphine
as a PN2 Ligand

Song-Eun Park; Seung Beom Kang; Kwang-Ju Jung; Ju-Eun Won; Sang-Gyeong Lee; Yong-Jin Yoon

doi:10.1055/s-0028-1083337

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Synthesis 2009(5): 815-823
DOI: 10.1055/s-0028-1083337

PAPER

Efficient Palladium-Catalyzed Amination of Aryl Chlorides Using Dicyclohexylamino[(2,6-dimethyl)morpholino]phenylphosphine as a PN₂ Ligand

Song-Eun Park^a, Seung Beom Kang^a, Kwang-Ju Jung^a, Ju-Eun Won^a, Sang-Gyeong Lee*^b, Yong-Jin Yoon*^a
^a Department of Chemistry & Environmental Biotechnology National Core Research Center, Research Institute of Natural Science, Graduate School for Materials and Nanochemistry, Gyeongsang National University, Jinju 660-701, Korea
^b Department of Chemistry & Research Institute of Natural Science, Graduate School for Materials and Nanochemistry, Gyeongsang National University, Jinju 660-701, Korea
Fax: +82(55)7610244; e-Mail: yjyoon@gnu.ac.kr;

Further Information

Publication History

Received 16 September 2008
Publication Date:
27 January 2009 (online)

Abstract
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Abstract

The palladium-catalyzed amination of aryl chlorides with various amines is accomplished using dicyclohexylamino[(2,6-dimethyl)morpholino]phenylphosphine as a bulky electron-rich monoaryl phosphine ligand. The optimized reaction conditions required the use of 1 mol% each of catalyst and ligand.

Key words

Buchwald-Hartwig amination - palladium-catalyzed amination - PN₂ ligand - palladium - C-N coupling

References

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24

Crystal data for ligand 1 (CCDC 716140): C₂₄H₃₉N₂OP, formula weight = 402.54, wavelength = 0.71073 Å, crystal system = monoclinic, space group = P2/n, unit cell dimensions: a = 16.3520 (9) Å, b = 8.1675 (5) Å, c = 17.9629 (10) Å, α = 90˚, β = 100.8710 (10)˚, γ = 90˚, volume = 2356.0(2) Å^³, Z = 4, density(calcd) = 1.135 mg/m^³, absorption coefficient = 0.133 mm^-¹, F(000) = 880, crystal size = 0.50 × 0.40 × 0.20 mm^³, θ range for data collection = 1.87 to 28.27˚, index ranges: -21 ≤ h ≤ 21, -10 ≤ k ≤ 9, -23 ≤ l ≤ 21, reflections collected = 14447, independent reflections = 5495 [R(int) = 0.0611], completeness to θ = 28.27˚ (94%), absorption correction = none, refinement method: full matrix least squares on F2, data/restraints/parameters = 5495/0/253, goodness-of-fit on F2 = 1.147, final R indices [I > 2σ(I)]: R1 = 0.0781, wR2 = 0.1620, R indices (all data): R1 = 0.0966, wR2 = 0.1700, largest diff. peak and hole: 0.560 and -0.440 eÅ^-³.

25

Crystal data for 11 (CCDC 716141): C₂₄H₃₉N₂O₂P, formula weight = 418.54, wavelength = 0.71073 Å, crystal system = tetragonal, space group = P4 (3), unit cell dimensions: a = 11.6762 (7) Å, b = 11.6762 (7) Å, c = 17.0457 (15) Å, α = 90˚, β = 90˚, γ = 90˚, volume = 2323.9 (3) Å^³, Z = 4, density(calcd) = 1.196 mg/m^³, absorption coefficient = 0.140 mm^-¹, F(000) = 912, crystal size = 0.30 × 0.20 × 0.20 mm^³, θ range for data collection = 1.74 to 25.99˚, index ranges = -14 ≤ h ≤ 14, -14 ≤ k ≤ 12, -18 ≤ l ≤ 21, reflections collected = 13286, independent reflections = 4071 [R(int) = 0.0456], completeness to θ = 25.99˚ (100%), absorption correction = none, refinement method = full matrix least squares on F2, data/restraints/parameters = 4071/1/262, goodness-of-fit on F2 = 1.238, final R indices [I > 2σ(I)] = R1 = 0.1017, wR2 = 0.2859, R indices (all data): R1 = 0.1065, wR2 = 0.2917, absolute structure parameter = 0.0(3), largest diff. peak and hole: 0.555 and -0.589 eÅ^-³.