Highly Selective Hydroaminomethylation of Internal Alkenes To Give Linear Amines

Ahmed, Moballigh; Bronger, Raymond P. J.; Jackstell, Ralf; Kamer, Paul C. J.; Leeuwen, Piet W. N. M. van; Beller, Matthias

doi:10.1002/chem.200600702

Cited by 99 publications

(41 citation statements)

References 82 publications

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“…The bite angles of the ligands have a dramatic effect on the both chemo-and regioselectivity of the reaction. Using XANTHPHOS-type or TETRABI ligands the HAM of internal alkenes can now be applied even to sophisticated substrates, showing a high versatility and large Scheme 6 HAM of internal olefines to linear amines [24] 126 E. Petricci and E. Cini applicability to the synthesis of different molecules [25]. When primary amines are used as nucleophiles, imines are isolated as the only product (Scheme 7).…”

Section: Hydroaminomethylation (Ham)mentioning

confidence: 98%

“…After a first contribution, the protocol developed was successfully modified with the screening of different ligands finally enabled the use of less drastic conditions in terms of reaction temperature, pressure of CO/H 2 , and reaction times with respect to the first proposed protocol (Table 2) [24]. The bite angles of the ligands have a dramatic effect on the both chemo-and regioselectivity of the reaction.…”

Section: Hydroaminomethylation (Ham)mentioning

confidence: 99%

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Domino Reactions Triggered by Hydroformylation

Petricci

Cini

2013

Topics in Current Chemistry

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Section: Hydroaminomethylation (Ham)mentioning

confidence: 98%

Section: Hydroaminomethylation (Ham)mentioning

confidence: 99%

Domino Reactions Triggered by Hydroformylation

Petricci

Cini

2013

Topics in Current Chemistry

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“…Hydroaminomethylation and each of its individual steps were monitored by high-pressure infrared spectroscopy. The results suggest that hydroaminomethylation takes place by a sequential isomerization/hydroformylation/amination/hydrogenation pathway [170].…”

mentioning

confidence: 92%

Carbonylation of Alkenes and Dienes

Kégl

2008

Modern Carbonylation Methods

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In the beginning, only cobalt catalysts were utilized for hydroformylation under relatively vigorous conditions. The moderate selectivity of the generally more desired linear isomers, the substantial formation of by-products, and the low stability of the catalysts forced more appropriate catalytic systems to be developed. Using donor ligands such as phosphanes resulted in an increase in the linear selectivity. Rhodium-containing catalysts, however, permitted the use of much milder conditions in combination with suitable ligands. Other transition metals such as ruthenium, palladium, platinum, and iridium also tended to show activity for hydroformylation, albeit a vast majority of works on hydroformylation still concentrated on rhodium-containing systems. Cobalt CatalystsThe initial rate of Co 2 (CO) 8 -catalyzed cyclohexene hydroformylation, triethyl orthoformate carbonylation, and CoH(CO) 4 formation from Co 2 (CO) 8 and H 2 is reduced by the addition of dinitrogen, argon, or xenon. It is assumed that the additional gas competes with one or more reactants for a coordinatively unsaturated site responsible for their activation, thus affecting the reaction rate [1].The carbonylation reaction of propylene oxide in the presence of various [Lewis acid] þ [Co(CO) 4 ] À salts was investigated using in situ attenuated total reflection infrared (ATR-IR) spectroscopy. b-Alkoxy-acyl-cobalttetracarbonyl species were found to be key intermediates from which two reaction routes start depending on the applied Lewis acid. Labile Lewis acid-alkoxy combinations primarily favor the production of lactone products [2].The reaction of olefins (1-octene, 3,3-dimethylbutene, cyclohexene) introduced into a preequilibrated Co 2 (CO) 8 þ H 2 system was investigated by high-pressure infrared spectroscopy. Based on the observed induction period for the formation of the corresponding aldehyde, the decrease in HCo(CO) 4 concentration and increase in Co 2 (CO) 8 concentration during the induction period, the active catalytic species of the type H x Co y (CO) z was proposed [3]. Experiments with isotope mixtures of H 2 /D 2 in the gas phase during the various steps of the reaction showed that the ratio of H/D isotopes in the hydrocarbon portion of the aldehyde product correlates with the HCo(CO) 4 /DCo(CO) 4 ratio in solution, whereas the RC(¼O)H/RC(¼O)D product ratio correlates with the H 2 /D 2 in the gas phase. It was concluded that the dominant pathway for the hydrogenolysis step in this type of hydroformylation is the direct reaction of hydrogen or deuterium with the acyl complex intermediate [4].The effect of argon (280 bar) on the rate of aldehyde formation in 1-hexene hydroformylation catalyzed by Co 2 (CO) 8 at 50 C, 70 bar P(CO) and 85 bar P(H 2 ) in toluene was investigated by high-pressure FT-IR spectroscopy. The initial rate of the reaction was found to be reduced by the presence of argon. A similar effect was observed in the RhH(CO)(PPh 3 ) 3 -catalyzed cyclohexene hydroformylation reaction [5]. 162j 7 Carbonylation of Alkenes and D...

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“…Since the regioselectivity of the hydroaminomethylation is implemented in the hydroformylation step, ligands that were developed for regioselective hydroformylation towards n-aldehydes, such as naphos or xantphos-type ligands, are promising candidates to be used in this reaction and are likely to give good regioselectivities. [6][7][8] However, there are still substantial problems to be overcome. In the case of ammonia and primary Scheme 1.…”

Section: Introductionmentioning

confidence: 99%

Hydroaminomethylation of n‐Alkenes in a Biphasic Ionic Liquid System

et al. 2008

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Hydroaminomethylation reactions were performed successfully in an imidazolium-based ionic liquid using a rhodium/sulfoxantphos system by reacting piperidine with different n-alkenes, affording yields higher than 95 % of the resulting amine with turnover frequencies of up to 16,000 h À1, along with high regioselectivity for the linear amines with l/b ratios up to 78. Additionally, facile quantitative catalyst recovery was accomplished and recycling of the catalyst and product separation was achieved by a fast phase separation after the reaction. The product distribution was monitored over time at different temperatures both in an organic solvent and in the ionic liquid in order to investigate and compare the course of the formation of (side) products and intermediates in these reactions. Furthermore, it was shown that the nature of the rhodium precatalyst has a profound effect on the activity and selectivity. Protic organic solvents and ionic liquids containing a C À H acidic bond in the imidazolium part have a beneficial effect on the hydrogenation activity of the catalyst systems.

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Highly Selective Hydroaminomethylation of Internal Alkenes To Give Linear Amines

Cited by 99 publications

References 82 publications

Domino Reactions Triggered by Hydroformylation

Domino Reactions Triggered by Hydroformylation

Carbonylation of Alkenes and Dienes

Hydroaminomethylation of n‐Alkenes in a Biphasic Ionic Liquid System

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