Synthesis of Primary Amines from Secondary and Tertiary Amines: Ruthenium‐Catalyzed Amination Using Ammonia

Bähn, Sebastian; Imm, Sebastian; Neubert, Lorenz; Zhang, Min; Neumann, Helfried; Beller, Matthias

doi:10.1002/chem.201100007

Cited by 50 publications

(16 citation statements)

References 74 publications

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“…Microwave-Assisted Synthesis of Hydroxycyclopentadienylruthenium Hydride Dimer (Shvo-Type) Complexes. The dinuclear complexes {[3,4-(R-C 6 H 4 ) 2 -2,5-Ph 2 (η 5 -C 4 CO)] 2 H}Ru 2 (CO) 4 (μ-H) [e.g., R = H, OMe, Cl] are typically prepared by heating Ru 3 (CO) 12 and tetraarylcyclopentadienones in MeOH for 40 h. An alternative two-step approach involves the synthesis of the precursor 3,4-(R-C 6 H 4 ) 2 -2,5-Ph 2 (η 4 -C 4 CO)Ru(CO) 3 , which is subsequently transformed to the corresponding dinuclear Shvo-type complex by a 48 h long reaction in acetone/water in the presence of Na 2 CO 3 . The latter method leads to lower yields and more difficult purification of the product.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Microwave-Assisted Synthesis of Functionalized Shvo-Type Complexes

et al. 2014

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A simple and expeditious microwave-assisted procedure for the synthesis of a variety of Shvo-type ruthenium complexes has been developed by reacting Ru 3 (CO) 12 with variously functionalized tetraarylcyclopentadienones under microwave irradiation in MeOH. Ligand precursors have also been prepared under microwave heating by a bis-aldol condensation of 1,3-diphenylacetone with variously functionalized aromatic diketones. All the reactions were very fast and clean, leading to good yields and purities.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Microwave-Assisted Synthesis of Functionalized Shvo-Type Complexes

et al. 2014

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“…Traditionally, the utilization of amines have focused on N−H functionalization, such as reductive aminations or cross-couplings [2,3], however, harnessing the C−N bond as a functional group for deamination transformations remains quite limited. Numerous methods for the preparation of primary amines by amination of alcohols, aldehydes, or halogenated hydrocarbons have been introduced [4][5][6], while the reverse reaction, a substitution of the amino group with a different nucleophile, such as direct conversion of amines to alcohols, is still challenging [7]. To achieve this, organic solvents and complex homogeneous catalysts are generally required for C−N functionalization [8].…”

Section: Introductionmentioning

confidence: 99%

Hydrothermal Water Enabling One-Pot Transformation of Amines to Alcohols

Wu¹,

Cheng²,

Wang³

et al. 2021

Preprint

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While the amination of primary alcohols to amines is quite normal, the reverse reaction, deamination of amines to alcohols is rare. Recent advances achieve the transformation by catalytic multistep processes. We report a one-pot method that enables water nucleophilic attack of amines through the unique catalytic role of hydrothermal water. By achieving dehydrogenation of amines or building targeting group, we fulfilled amines transformation by subsequent reduction or direct deamination, which could further link to the utilization of naturally abundant glutamic acid. The method avoids oxidants, catalysts or multistep, thus achieves simple, green and selective transformation of primary amines.

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“…One of the most pursued targets concerns C–N bond formation directly with ammonia, a phenomenon that is often hampered by the intrinsic nature of the substrate. However, remarkable advances have been made in this context, and well‐designed late‐metal‐based catalysts have been optimized to allow the catalytic C–N coupling between ammonia and a number of functionalized compounds such as alcohols, alkynes, ketones, amines, and allylic substrates affording new N‐containing functionalized compounds directly from ammonia.…”

Section: Introductionmentioning

confidence: 99%

C–N Bond Coupling Reactions of Ammonia with Acetone Promoted by Iridium and Rhodium Complexes: Experimental and DFT Studies

et al. 2016

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Treatment of acetone solutions of the known chlorido‐bridged complexes [{M(µ‐Cl)(cod)}2] (M = Ir, Rh; cod = 1,5‐cyclooctadiene) under an ammonia atmosphere afforded the cationic complexes {M(cod)[κN,κN‐NH2–C(CH3)2–CH2–C(CH3)=NH]}Cl [M = Ir (3), Rh (4)]. The molecular structures of 3 and 4 showed the formation of six‐membered metallacycles due to the presence of a 4‐imino‐2‐methylpentan‐2‐amine‐κN,κN‐chelated ligand. Alternatively, the cations [M(cod)(NCCH3)2]BF4 (M = Ir, Rh) reacted with gaseous ammonia at atmospheric pressure affording bis(ammine) complexes [M(cod)(NH3)2]BF4 [M = Ir (5), Rh (6)], which were found to react with acetone, forming cations [M(cod)(κN,κN‐NH2–C(CH3)2–CH2–C(CH3)=NH)]BF4 [M = Ir (7), Rh (8)]. DFT studies reveal that the transformation of 6 into 8 is mediated by NH3 molecules acting as an external base. The reaction is triggered by deprotonation of an ammonia ligand forming a amido–metal intermediate, which further transforms into an acetimino ligand through aldol condensation. The terminal methyl group of one acetimino ligand is deprotonated by NH3 yielding an enamine ligand, which can react with the imine ligand through concerted nucleophilic addition to afford the metallacycle, which is stabilized by protonation.

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Synthesis of Primary Amines from Secondary and Tertiary Amines: Ruthenium‐Catalyzed Amination Using Ammonia

Abstract: Der Duft des Erfolges: Wertvolle ungesättigte Moschus‐Duftstoffe mit 15‐gliedrigem Makrocyclus wie 2 wurden in einer stereokontrollierten Reaktion durch zwei aufeinander folgende Fragmentierungen hergestellt, ausgehend vom tricyclischen Dihydroxyketon 1.

Cited by 50 publications

References 74 publications

Microwave-Assisted Synthesis of Functionalized Shvo-Type Complexes

Microwave-Assisted Synthesis of Functionalized Shvo-Type Complexes

Hydrothermal Water Enabling One-Pot Transformation of Amines to Alcohols

C–N Bond Coupling Reactions of Ammonia with Acetone Promoted by Iridium and Rhodium Complexes: Experimental and DFT Studies

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