Ruthenium-catalyzed reductive deamination and tandem alkylation of aniline derivatives

Koreeda, Tetsuro; Kochi, Takuya; Kakiuchi, Fumitoshi

doi:10.1016/j.jorganchem.2013.06.001

Cited by 29 publications

(16 citation statements)

References 23 publications

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“…Very few methods are available for the cleavage of C(aryl)-N bond. 2,3 The deamination intermediates reacted further in the reaction conditions to yield Questiomycin-A which is a novel synthetic reductive method for the synthesis of the pharmaceutically interesting class of 2-aminophenoxazin-3-one. We believe the method disclosed is suitable for the synthesis of several related 2-aminophenoxazin-3-one derivatives.…”

Section: Resultsmentioning

confidence: 99%

“…Recently reductive deamination of o-acylaniline derivatives was achieved by heating the reaction with the catalyst RuH 2 (CO)(PPh 3 ) 3 . 3 But this method is applicable to limited substrates containing ortho directing group. Further, cleavage of C(aryl)-N bonds requires either expensive reagents 2 or harsh conditions.…”

mentioning

confidence: 99%

“…Further, cleavage of C(aryl)-N bonds requires either expensive reagents 2 or harsh conditions. 3 Therefore, there is a demand to develop methods for deamination reactions to prepare important organic synthons. Herein we report one pot C (aryl)-N bond cleavage (catalytic deamination) of two Buchwald products 5A and 5B with Pd/C under the atmosphere of Hydrogen in methanol followed by Questiomycin A formation.…”

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confidence: 99%

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Unexpected one pot C (aryl)–N bond cleavage and Questiomycin A formation from the reduction reaction of 2-amino-6-nitrophenol derivatives

Mustafa

Reddy

Babu

2015

Tetrahedron Letters

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Section: Resultsmentioning

confidence: 99%

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confidence: 99%

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confidence: 99%

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Unexpected one pot C (aryl)–N bond cleavage and Questiomycin A formation from the reduction reaction of 2-amino-6-nitrophenol derivatives

Mustafa

Reddy

Babu

2015

Tetrahedron Letters

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“…For these compounds, such as palmitamide, hexadecanenitrile and stearonitrile, HDN is an effectual means for converting them into hydrocarbons [90][91][92]. However, the rupture of C-N bond-breaking rings is very difficult to achieve in aromatic nitrogen compounds even under drastic conditions.…”

Section: Hdn Of Main Nitrogen Compounds In Biocrudementioning

confidence: 99%

Review of Denitrogenation of Algae Biocrude Produced by Hydrothermal Liquefaction

Sun

Yang

Shi³

2017

Trans. Tianjin Univ.

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Recently, algae biocrude has drawn considerable attention as algae are considered to be one of the major fuel feedstocks of the future. Based on some impressive results achieved under appropriate conditions, the algae hydrothermal liquefaction (HTL) process has proven to be energy efficient. However, the HTL of biocrude is characterized by a high nitrogen content, which prevents its use in the field of transportation due to the associated nitrogen oxide emissions. Despite this toxicity, few research efforts have focused on the denitrogenation of algae biocrude. In this study, we review the effect of different strain-specific operation parameters and process upgrades with respect to the nitrogen content of biocrude. To achieve denitrogenation, chemical engineering may be required, although some improvements in biocrude properties have been achieved in a number of process upgrades. The use of similar successful pathways has the potential to improve the field of HTL biocrude denitrogenation. These methods, including the adsorptive and extractive denitrogenations of fossil fuels and the hydrodenitrogenation of the main nitrogen compounds, are helpful for developing a better understanding of the potential of denitrogenation for algae HTL biocrude. We also recommend the use of some available catalysts and corresponding operation parameters to promote continued research on denitrogenation.

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“…[1,2] Our group has reported ruthenium-catalyzed functionalizations of aromatic ketones with organoboronates through the cleavage of carbon-hydrogen and carbon-heteroatom bonds by oxidative addition. [3][4][5][6][7][8] In these reactions,s imple carbonyl groups,w hich are useful for further transformations,e ffectively function as directing groups by forming ac helate and selectively convert the unreactive bonds at the ortho-positions of the aryl ring into carbon-carbon bonds.I nm any cases,h owever, selective monofunctionalization is difficult for substrates bearing more than one ortho carbon-hydrogen or carbon-oxygen bond. [9] Forexample,the reaction of 2',6'-dimethoxyacetophenone (1) with arylboronates in the presence of ac atalytic amount of [RuH 2 (CO)(PPh 3 ) 3 ]g ave the diarylation products as major products,a nd it is indicated that the second CÀOb ond cleavage is faster than the dissociation of the monoarylation product from the catalyst (Scheme 1a).…”

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confidence: 99%

Ruthenium‐Catalyzed Monoalkenylation of Aromatic Ketones by Cleavage of Carbon–Heteroatom Bonds with Unconventional Chemoselectivity

et al. 2015

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Ruthenium-catalyzed selective monoalkenylation of ortho CÀOo rC ÀNb onds of aromatic ketones was achieved. The reaction allowed the direct comparison of the relative reactivities of the cleavage of different carbon-heteroatom bonds,t hus suggesting an unconventional chemoselectivity, where smaller,more-electron-donating groups are more easily cleaved. Selective monofunctionalization of C À Obonds in the presence of ortho CÀHb onds was also achieved.Transition-metal-catalyzed carbon-carbon bond-formation by selective cleavage of unreactive bonds has been extensively investigated because it allows transformations with unconventional chemoselectivity. [1, 2] Our group has reported ruthenium-catalyzed functionalizations of aromatic ketones with organoboronates through the cleavage of carbon-hydrogen and carbon-heteroatom bonds by oxidative addition. [3][4][5][6][7][8] In these reactions,s imple carbonyl groups,w hich are useful for further transformations,e ffectively function as directing groups by forming ac helate and selectively convert the unreactive bonds at the ortho-positions of the aryl ring into carbon-carbon bonds.I nm any cases,h owever, selective monofunctionalization is difficult for substrates bearing more than one ortho carbon-hydrogen or carbon-oxygen bond. [9] Forexample,the reaction of 2',6'-dimethoxyacetophenone (1) with arylboronates in the presence of ac atalytic amount of [RuH 2 (CO)(PPh 3 ) 3 ]g ave the diarylation products as major products,a nd it is indicated that the second CÀOb ond cleavage is faster than the dissociation of the monoarylation product from the catalyst (Scheme 1a).[5a]Herein we report that selective monoalkenylation of ortho carbon-heteroatom bonds of aromatic ketones was achieved for the ruthenium-catalyzed reaction with alkenylboronates (Scheme 1b). This work allowed direct comparison of the relative ease of the cleavage of different carbonheteroatom bonds,a nd it is suggested that smaller,m oreelectron-donating groups are more easily cleaved (Scheme 1c), aphenomenon which is unconventional for reactions proceeding by oxidative addition to transition metals.S elective monofunctionalization of C À Ob onds in the presence of ortho C À Hb onds is also found to be possible for benzophenone derivatives (Scheme 1d).First, we examined the ruthenium-catalyzed CÀOa lkenylation [5a, 11] of 1 with the styrylboronate 2a (Table 1). When the reaction of 1 was performed with 2equivalents of 2a in the presence of 4mol %of[RuH 2 (CO)(PPh 3 ) 3 ]at140 8 8Cinp-xylene for 8hours,a lkenylation of the C À Ob ond proceeded to give the monoalkenylation product 3a in 57 %y ield (NMR) along with 6% yield (NMR) of dialkenylation product 4a (entry 1). Theo bserved selectivity toward the monoalkenylation is in contrast with the CÀOa rylation of 1,[5a] which mainly affords diarylation products (Scheme 1a). Our group reported that the reaction of 2'-methoxyacetophenone,w hich has both ortho C À Ha nd C À Ob onds,w ith alkenylboronates in the presence of ac atalytic amount of [RuH 2 (CO)(PP...

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Ruthenium-catalyzed reductive deamination and tandem alkylation of aniline derivatives

Cited by 29 publications

References 23 publications

Unexpected one pot C (aryl)–N bond cleavage and Questiomycin A formation from the reduction reaction of 2-amino-6-nitrophenol derivatives

Unexpected one pot C (aryl)–N bond cleavage and Questiomycin A formation from the reduction reaction of 2-amino-6-nitrophenol derivatives

Review of Denitrogenation of Algae Biocrude Produced by Hydrothermal Liquefaction

Ruthenium‐Catalyzed Monoalkenylation of Aromatic Ketones by Cleavage of Carbon–Heteroatom Bonds with Unconventional Chemoselectivity

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