A direct route to medium and large cyclic amines from aminoalkenes

Bergmann, David; Campi, Eva M.; Jackson, W. Roy; Patti, Antonio F.; Saylik, Dilek

doi:10.1016/s0040-4039(99)01020-5

Cited by 18 publications

(9 citation statements)

References 12 publications

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“…111 Otherwise, the intramolecular reaction of aminoalkenes produces the corresponding cycloamines using mono-or bisphosphites, such as Biphephos (L20), containing very crowded bulky aryl substituents (Scheme 16). 112,113 This L20 ligand also generates with [Rh(acac)(CO) 2 ] an efficient catalytic system to perform the HAM reaction of 3-allyl-2-methylquinazolin-4(3H)-one with arylhydrazines. 114 Similarly, the [Rh(acac)(CO) 2 ]/diphosphite L21 catalytic system allows the highly regioselective synthesis of two biologically active targets to be performed, 115,116 the antiarrhythmia ibutilide 117 and the antidepressant aripiprazole 118 (Scheme 17).…”

Section: Chemical Reviewsmentioning

confidence: 99%

“…Otherwise, the intramolecular reaction of aminoalkenes produces the corresponding cycloamines using mono- or bisphosphites, such as Biphephos ( L20 ), containing very crowded bulky aryl substituents (Scheme ). , This L20 ligand also generates with [Rh(acac)(CO) 2 ] an efficient catalytic system to perform the HAM reaction of 3-allyl-2-methylquinazolin-4(3 H )-one with arylhydrazines …”

Section: Mechanism and Selectivitymentioning

confidence: 99%

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Tandem Hydroaminomethylation Reaction to Synthesize Amines from Alkenes

2018

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In the context of atom economy and low environmental impact, synthesis of amines by an efficient catalytic process is of great importance to produce these building blocks for fine chemical industry. The one-pot hydroaminomethylation of alkenes is a tandem reaction which involves three successive steps under CO/H pressure to perform the catalyzed hydroformylation of the alkene into the corresponding aldehyde followed by its condensation with a N-H function and the catalyzed hydrogenation of the imine/enamine intermediate into the corresponding saturated amine. Rhodium and more recently ruthenium complexes have been designed to combine high conversions of the reactants and chemoselectivity in the expected amines with high regioselectivity in either the linear or the branched amine. The coordination sphere of the metal according to the presence of ligands, temperature, CO/H partial pressures, and nature of the solvent is essential for complying with these selectivity requirements. The rate of the hydroformylation step needs to be fast with regard to the hydrogenation step. The role of amines in the coordination sphere and water, presumably in the second sphere, on the mechanism requires some more studies. Similarly, the enantioselective synthesis of amine is not yet achieved directly and interrupted processes or use of asymmetric organo-catalyzed reductive amination are efficient synthetic ways for producing chiral amines. The separation of the catalyst from the organic products by biphasic or (semi-) heterogeneized systems and its recycling have been demonstrated in many cases. The present review provides a report of the state of the art in this autotandem hydroaminomethylation catalysis and should open prospects in the design of less expensive and abundant metal complexes for reaching at low cost similar and even superior performances.

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Section: Chemical Reviewsmentioning

confidence: 99%

Section: Mechanism and Selectivitymentioning

confidence: 99%

Tandem Hydroaminomethylation Reaction to Synthesize Amines from Alkenes

2018

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“…Furthermore some diphosphite ligands gave interesting results in the hydrogenation, for instance in hydrogenation of dimethyl itaconate or methyl (Z)-2-acetamidocinnamate. However, a few studies report [27,28] the cyclohydrocarbonylation of aminoalkenes to produce the corresponding cycloamines. However, a few studies report [27,28] the cyclohydrocarbonylation of aminoalkenes to produce the corresponding cycloamines.…”

Section: Phosphite Ligandsmentioning

confidence: 99%

“…[26] Although these ligands seem attractive for the hydroaminomethylation reaction, they have often been considered [16] as unsuitable and not able to promote the reaction, due to their sensitivity to hydrolysis. However, a few studies report [27,28] the cyclohydrocarbonylation of aminoalkenes to produce the corresponding cycloamines. The ligands used in these reports are mono-or bisphosphites, such as Biphephos (24), containing very crowded aryl substituents (Scheme 9).…”

Section: Phosphite Ligandsmentioning

confidence: 99%

Recent Advances in Amine Synthesis by Catalytic Hydroaminomethylation of Alkenes

2011

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Carbon–carbon coupling catalyzed by transition metals represents a powerful synthetic method to have an access to organic molecules, especially when they present a significant complexity. The strategy to transform abundant and not expensive reactants into products of pharmaceutical interest by the appropriate catalytic way is of fundamental interest, provided that high conversion rates and selectivities can be gained. During the past decade, considerable progress has been made to transform a simple alkene into an aldehyde by carbonylation, to condense it with an NH function‐containing molecule present in the medium, and to hydrogenate the resulting imine or enamine into the relevant amine. Rhodium complexes are able to catalyze this series of reactions and be an efficient synthetic tool to produce rather sophisticated amines in one‐pot reactions under mild conditions of pressure and temperature. In the future, the production of various amines required by the industry of fine chemicals looks attractive by means of this catalytic method.

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“…The rhodium-catalyzed hydroformylation of a range of aminoalkenes to give medium-and large-ring cyclic amines has been reported (Scheme 96). 190 Treatment of 311 with H 2 -CO (ratio between 9 : 1 and 1 : 5) gave the cyclic amine 312 in good to excellent yield (particularly for smaller ring sizes) but also significant quantities of the aminoalkane 313.…”

Section: Medium and Large Ringsmentioning

confidence: 99%