Highly Selective Synthesis of Carboxamides via Transition Metal Catalysed Aminocarbonylation

Kiss, Mercédesz; Takács, Attila; Kollár, László

doi:10.2174/2213346102666150213212458

Cited by 26 publications

(9 citation statements)

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“…As expected for the aminocarbonylation of iodo‐aromatics, both single and double carbon monoxide insertion took place resulting in the formation of carboxamide ( 2a , 2b ) and 2‐ketocarboxamide ( 3a , 3b ) products. It has been proved by ESR studies that the N ‐oxyl functionality was partially preserved during the catalytic reaction showing all monoradicals a triplet line (a N = 15.5 G).…”

Section: Resultsmentioning

confidence: 59%

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4‐Amino‐TEMPO as N‐Nucleophile in Palladium‐Catalyzed Aminocarbonylation

Gergely

Takács²,

Kollár

2016

Journal of Heterocyclic Chem

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Palladium‐catalyzed aminocarbonylation of iodobenzene and iodoalkenes (1‐iodocyclohexene, 4‐tert‐butyl‐1‐iodocyclohexene, α‐iodostyrene, 17‐iodoandrost‐16‐ene) was carried out using a free radical (4‐amino‐TEMPO) for the first time. Its reduced form (4‐amino‐2,2,6,6‐tetramethylpiperidine) was also used as N‐nucleophile. The free radical was partially reduced under aminocarbonylation conditions; however, the isolation of carbonylated products bearing a stable radical moiety was successfully accomplished. It was proved that the reduction of the 1‐oxyl functionality took place to higher extent when more severe conditions (40 bar CO pressure) were used. The mixture of carboxamide and 2‐ketocarboxamide products was obtained using iodobenzene because of single and double carbon monoxide insertion, respectively. In turn, carboxamide derivatives were formed exclusively when iodoalkenes were used as substrates.

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Section: Resultsmentioning

confidence: 59%

“…That is, amino acid esters or ester functionalised piperidines may serve as primary and secondary amines in the aminocarbonylation. Several α,β‐unsaturated carboxamides, aromatic carboxamides, or aromatic 2‐ketocarboxamides were synthesized in single and double carbon monoxide insertion, respectively .…”

Section: Introductionmentioning

confidence: 99%

4‐Amino‐TEMPO as N‐Nucleophile in Palladium‐Catalyzed Aminocarbonylation

Gergely

Takács²,

Kollár

2016

Journal of Heterocyclic Chem

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“…Azabicyclo[3.2.1]octan-3-one (nortropinone) ( a ) and 3α-hydroxy-8-azabicyclo[3.2.1]octane (nortropine) ( b ) as N -nucleophiles were applied for the aminocarbonylation of iodoalkenes (such as 1-iodocyclohexene ( 1 ), 4- tert -butyl-1-iodocyclohexene ( 2 ), trans -1-iodo-1-octene ( 3 ), 17-iodoandrost-16-ene ( 4 ), and 2-iodobornene ( 5 )) in the presence of palladium catalysts ( Scheme 1 ). Based on the prior knowledge of our research group [ 65 , 66 ], a low-ligated, highly active Pd(0) catalyst, prepared in situ from Pd(OAc) 2 and PPh 3 , was used. The reduction of Pd(II) to catalytically active, highly unsaturated Pd(0) species took place on the influence of the phosphine while it is oxidized to phosphine oxide [ 67 , 68 , 69 ].…”

Section: Resultsmentioning

confidence: 99%

Selective Synthesis of N-Acylnortropane Derivatives in Palladium-Catalysed Aminocarbonylation

et al. 2021

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The aminocarbonylation of various alkenyl and (hetero)aryl iodides was carried out using tropane-based amines of biological importance, such as 8-azabicyclo[3.2.1]octan-3-one (nortropinone) and 3α-hydroxy-8-azabicyclo[3.2.1]octane (nortropine) as N-nucleophile. Using iodoalkenes, the two nucleophiles were selectively converted to the corresponding amide in the presence of Pd(OAc)2/2 PPh3 catalysts. In the presence of several iodo(hetero)arenes, the application of the bidentate Xantphos was necessary to produce the target compounds selectively. The new carboxamides of varied structure, formed in palladium-catalyzed aminocarbonylation reactions, were isolated and fully characterized. In this way, a novel synthetic method has been developed for the producing of N-acylnortropane derivatives of biological importance.

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“…The low reactivity of the less basic aromatic amine (b) is not surprising in the light of earlier results obtained with a great variety of iodoalkenes. In general, the secondary amines, especially k show lower reactivity than the primary amines (Schoenberg and Heck 1974a, b, Schoenberg et al 1974, Skoda-Földes et al 2002, Kiss et al 2015. Using these steroidal iodoalkene substrates (20-iodo-20-pregnenes) this effect is even more pronounced.…”

Section: Synthesis Of 20-carboxamido-20-enes Via Palladium-catalysed mentioning

confidence: 97%

“…Even the importance of the double carbon monoxide insertion resulting in 2-ketocarboxamides (Ozawa et al 1984;Son et al 1988) has been emphasised, i.e., the chemoselectivity towards 2-ketocarboxamides/carboxamides is an important issue. However, the aminocarbonylation of iodoalkenes/ enol triflates is a chemoselective reaction providing unsaturated carboxamides only (Kiss et al 2015). The double carbon monoxide insertion, i.e., the formation of unsaturated ketocarboxamides requires special triarylphosphitebased palladium catalysts (Carrilho et al 2012).…”

Section: ) Provided a Solidmentioning

confidence: 99%

Synthesis of novel pregnane-based 20-carboxamides via palladium-catalysed aminocarbonylation

et al. 2021

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Abstract20-Carboxamidopregnene derivatives, such as 3β-acetoxy-5α-pregn-20-ene-20-carboxamides and 5α-pregn-20-ene-20-carboxamides were synthesized from the widely accessible 3β-acetoxy-pregn-5,16-dien-20-one (PDA) using selective hydrogenation, hydrazine and iodoalkene formation, as well as palladium-catalysed aminocarbonylation. The 20-iodo-20-ene derivatives, obtained from the corresponding 20-keto derivatives via their hydrazones, served as substrates. 23 new 20-carboxamides were obtained using various N-nucleophiles ranging from simple primary amines to α-amino acid esters. The novelty of this methodology lies in the application of facile, moderate or high-yielding reactions to obtain otherwise hardly accessible steroidal 20-carboxamides of pharmaceutical importance. In other words, instead of the enzymatic or synthetic degradation of e.g., sterols or cholanic acids, functionalization of the basic skeleton (a ‘building-up’ approach) was used.

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Highly Selective Synthesis of Carboxamides via Transition Metal Catalysed Aminocarbonylation

Cited by 26 publications

References 0 publications

4‐Amino‐TEMPO as N‐Nucleophile in Palladium‐Catalyzed Aminocarbonylation

4‐Amino‐TEMPO as N‐Nucleophile in Palladium‐Catalyzed Aminocarbonylation

Selective Synthesis of N-Acylnortropane Derivatives in Palladium-Catalysed Aminocarbonylation

Synthesis of novel pregnane-based 20-carboxamides via palladium-catalysed aminocarbonylation

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