Base‐Catalyzed Hydroamination of Olefins: An Environmentally Friendly Route to Amines

Seayad, Jayasree; Tillack, Annegret; Hartung, Christian G.; Beller, Matthias

doi:10.1002/chin.200303229

Cited by 5 publications

(5 citation statements)

References 17 publications

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“…(S)-Mosher acid was converted into the corresponding (R)-Mosher acid chloride according to the literature procedure. 39 The hydroamination products 2-methyl-4,4-diphenylpyrrolidine (4a), 38a 3methyl-2-azaspiro [4,5]decane (4b), 40a 2-methylpyrrolidine (4c), 25 2,4,4-trimethylpyrrolidine (4d), 25 2-methyl-5,5-diphenylpiperidine ( 6), 38a 2-methyl-6,6-diphenylazepane ( 8), 40b,c 2-benzyl-4,4-diphenylpyrrolidine (10), 38e 1-benzyl-2,4,4-trimethylpyrrolidine (12a), 38b Nbenzyl-2-methyl-4,4-diphenylpyrrolidine (12b), 38b 2-(but-3-en-1-yl)-5-methylpyrrolidine ( 14), 30b 3,5-dimethylhexahydro-1H-pyrrolizine ( 15), 30b N-benzylheptan-2-amine (16), 14b,41a N-benzyloctan-2amine ( 17), 14b,41b N-benzyl-4-phenylbutan-2-amine (18), 14b,41a and N-(4-methoxybenzyl)-4-phenylbutan-2-amine (19) 14b,41c are known compounds and were identified by comparison to the literature NMR spectroscopic data.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Asymmetric Intra- and Intermolecular Hydroamination Catalyzed by 3,3′-Bis(trisarylsilyl)- and 3,3′-Bis(arylalkylsilyl)-Substituted Binaphtholate Rare-Earth-Metal Complexes

et al. 2018

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The series of novel 3,3′-bis(trisarylsilyl)-and 3,3′-bis(arylalkylsilyl)-substituted binaphtholate rare-earthmetal complexes 2a−i (SiR 3 = Si(o-biphenylene)Ph (a), SiCyPh 2 (b), Si-t-BuPh 2 (c), Si(i-Pr) 3 (d), SiCy 2 Ph (e), Si(2-tolyl)Ph 2 (f), Si(4-t-Bu-C 6 H 4 ) 3 (g), Si(4-MeO-C 6 H 4 )Ph 2 (h), SiBnPh 2 (i)) have been prepared via arene elimination from [Ln(o-C 6 H 4 CH 2 NMe 2 ) 3 ] (Ln = Y, Lu) and the corresponding 3,3′-bis(silyl)-substituted binaphthol. The complexes exhibit high catalytic activity in the hydroamination/ cyclization of aminoalkenes, with activities exceeding 1000 h −1 for (R)-2f-Ln, (R)-2g-Ln, and (R)-2h-Ln in the cyclization of 2,2-diphenylpent-4-enylamine (3a) at 25 °C, while the rigid dibenzosilole-substituted complexes (R)-2a-Ln and the triisopropylsilyl-substituted complexes (R)-2d-Ln exhibited the lowest activity in the range of 150−270 h −1 . Catalysts (R)-2b-Lu, (R)-2c-Lu, (R)-2f-Lu, and (R)-2i-Lu provide the highest selectivities for the majority of the substrates, while the yttrium congeners are usually less selective. The highest enantioselectivities of 96% ee were observed using (R)-2a-Lu and (R)-2c-Lu in the cyclization of (4E)-2,2,5-triphenylpent-4-enylamine (9). The reactions show apparently zero-order rate dependence on substrate concentration and first-order rate dependence on catalyst concentration, with some reactions exhibiting a slightly accelerated rate at high conversion due to a shift in the equilibrium between a less active, higher coordinate catalyst species in favor of a more active, lower coordinate species as a result of weaker binding of the hydroamination product in comparison to the aminoalkene substrate. The shift in equilibrium from the higher to the lower coordinate species is also entropically favored at elevated temperatures, which results in an unusual increase in selectivity in the cyclization of 2,2-dimethylpent-4-enylamine (3d), presumably due to a higher selectivity of the lower coordinate catalyst species. All binaphtholate yttrium complexes, except (R)-2a-Y, are catalytically active in the intermolecular hydroamination of benzylamines with terminal alkenes. The highest selectivity of 66% ee was observed for the reaction of benzylamine with 4-phenyl-1-butene using (R)-2h-Y at 110 °C.

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Section: ■ Experimental Sectionmentioning

confidence: 99%

Asymmetric Intra- and Intermolecular Hydroamination Catalyzed by 3,3′-Bis(trisarylsilyl)- and 3,3′-Bis(arylalkylsilyl)-Substituted Binaphtholate Rare-Earth-Metal Complexes

et al. 2018

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“…Alkene hydroamination, while not unprecedented in biosynthetic pathways, is an uncommon reaction in the cell, and also in the reaction flask. Although this powerful reaction has the potential to form skeletal C–N bonds and two stereocenters via net isomerization of bonding, it represents an underutilized approach toward alkaloid synthesis (not considering amine conjugate addition), due mainly to the insufficiency of tools available to the synthetic chemist in this area, especially compatibility with functional groups. , For example, the earliest reactions involved heating alkali metal salts of ammonia with alkenes to form alkylamines. − …”

Section: General Strategies: Historical Threadsmentioning

confidence: 99%

A Longitudinal Study of Alkaloid Synthesis Reveals Functional Group Interconversions as Bad Actors

Crossley

Shenvi

2015

Chem. Rev.

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“…Compared to conventional methods of amine synthesis like nucleophilic substitutions, catalytic reactions might avoid the production (of stoichiometric amounts) of salts. Hence, hydroamination [89][90][91][92] and hydroaminomethylation [93] (Fig. 7) are perfectly suited to synthesize amines and fulfill today's needs of "green chemistry" [94].…”

Section: Perspectives For the Use Of Renewables And Model Examplesmentioning

confidence: 99%

A personal view on homogeneous catalysis and its perspectives for the use of renewables

Beller

2008

Euro J Lipid Sci & Tech

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This personal account is based on a talk at the conference "Fats and Oils as Renewable Feedstock for the Chemical Industry" in Emden, Germany. It describes selected perspectives and challenges applying catalysis for the refinement of renewables. Because the author himself has not been active in the past using biomass-based starting materials, special focus is given on the use of homogeneous catalysis as a tool for a more sustainable chemistry in industry and academia. Recent developments of catalysts in our research group are used to illustrate the current status and challenges of homogeneous catalysis in this area.

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Base‐Catalyzed Hydroamination of Olefins: An Environmentally Friendly Route to Amines

Abstract: For Abstract see ChemInform Abstract in Full Text.

Cited by 5 publications

References 17 publications

Asymmetric Intra- and Intermolecular Hydroamination Catalyzed by 3,3′-Bis(trisarylsilyl)- and 3,3′-Bis(arylalkylsilyl)-Substituted Binaphtholate Rare-Earth-Metal Complexes

Asymmetric Intra- and Intermolecular Hydroamination Catalyzed by 3,3′-Bis(trisarylsilyl)- and 3,3′-Bis(arylalkylsilyl)-Substituted Binaphtholate Rare-Earth-Metal Complexes

A Longitudinal Study of Alkaloid Synthesis Reveals Functional Group Interconversions as Bad Actors

A personal view on homogeneous catalysis and its perspectives for the use of renewables

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