New synthesis of nitrogen heterocycles through amide-directed hydrocarbonylation of alkenamides catalyzed by rhodium complexes

Ojima, Iwao; Korda, Anna; Shay, William R.

doi:10.1021/jo00006a013

Cited by 66 publications

(20 citation statements)

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“…Increasing the catalyst loading of XPhos-Pd-G2 to 1 mol % was sufficient for the cross-coupling of N -benzyl-2-chloroacetamide 4a with various alkenyltrifluoroborates as shown in Table 2. An allylic amide that has been demonstrated to be an important substrate in domino hydrocarbonylation reactions 18 and ring-closing metathesis 19 was obtained in good yields (Table 2, entry 5).…”

mentioning

confidence: 99%

Pd-Catalyzed Cross-Coupling of Potassium Alkenyltrifluoroborates with 2-Chloroacetates and 2-Chloroacetamides

2013

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mentioning

confidence: 99%

Pd-Catalyzed Cross-Coupling of Potassium Alkenyltrifluoroborates with 2-Chloroacetates and 2-Chloroacetamides

2013

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“…Використання комп-лексного каталізатора 1 направляє реакцію у бік утворення δ-лактаму, у той же час застосування каталізатора 2 генерує утворення біциклічного продукту 50 [28] (схема 19).…”

Section: схемаunclassified

Heterocyclization of amides of alkenylcarboxylic acids

Tsyzoryk¹,

Васькевич²,

Вовк³

2015

J. org. pharm. chem.

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(Ховейда, Граббса, Нолана), реакції мета-тезису, а також радикальних процесів у регіо-та стереоселективних циклізаціях амідів у м'яких умовах. Розглянуті синтетичні варіанти носять загальний характер і дозволяють поряд із процесами циклізації здійснювати спрямовану функціоналізацію O-, N-, S-вмісних малих та середніх гетероциклічних систем. HETEROCYCLIZATION OF AMIDES OF ALKENYLCARBOXYLIC ACIDS N.M.Tsyzoryk, A.I.Vaskevich, M.V.Vovk Key words: amides of alkenylcarboxylic acids; electrophilic intramolecular cyclization; lactones; lactams The latest published data on heterocyclization of amides of alkenylcarboxylic acids have been systematized. It has been proven that the electrophilic intramolecular cyclization reaction of functionally substituted olefins opened in the 70s of the last century is a convenient way of constructing different oxygen-, nitrogen-and sulfurcontaining heterocyclic compounds. It has been noted that anilides of unsaturated carboxylic acids as bifunctional nucleophilic systems containing alkenyl and aminocarbonyl functions are useful models to study the electrophilic cyclization reaction, which leads to formation of O-and N-containing heterocycles (lactones and lactams). The last of them belong to the important types of compounds used as key blocks in the synthesis of biologically active alkaloids and their analogues, pharmaceutical and agrochemical products. The effective approaches to the synthesis of new types of functionalized lactones and lactams have been developed; amides of 3-butenoic, 4-pentenoic and 5-hexenoic acids are often used as substrates for their design. Along with classical methods of synthesis of lactones and lactams the literary sources relating to the use of original catalytic electrophilic systems (Nolan, Grubbs, Hoveyda), the metathesis reaction and radical processes in regio-and stereoselective cyclization of amides under mild conditions have been analyzed and summarized in the article. The synthetic versions considered are general in nature and allow to perform the targeted functionalization of O-, N-, S-containing heterocyclic small and medium-sized systems along with the cyclization processes. ГЕТЕРОЦИКЛИЗАЦИИ АМИДОВ АЛКЕНИЛКАРБОНОВЫХ КИСЛОТ

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“…Nitrogen derivatives are often capable of doing this: hydroformylation of 4-pentenamide 4.163 yielded dihydropyridone 4.164 due to coordination of the carbonyl oxygen to rhodium (Scheme 4.60), 63 Oxygen atoms, such as in an alcohol, are not sufficiently good ligands to have this effect. If the substrate is an aliphatic alkene, the ligand can then direct rhodium to the internal position.…”

Section: Directed Hydroformylationmentioning

confidence: 99%

Carbonylation

2012

Organic Synthesis Using Transition Metals

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Carbon monoxide, with the use of transition-metal catalysis, has become a valuable C1 building block. 1 Carbonylation is one method of intercepting the palladium intermediates generated by oxidative addition. 2 If the reaction is run under at atmosphere of carbon monoxide, then the palladium intermediate may undergo CO insertion, generating an 1 -acyl complex, before any other reagent (Scheme 4.1). Whether it will do so in useful quantities is a question of kinetics: will the rate of CO insertion be faster than the rates of the other possible processes? The reactivity of the other reagents may be reduced by careful choice of functionality, or their concentration may be reduced by slow addition, perhaps by use of a syringe pump. The rate of reactions involving carbon monoxide may be increased by the use of higher pressures. While many reactions proceed satisfactorily at atmospheric pressure, other reactions require increased pressures. Pressures up to 100 psi may be safely attained in good quality, heavy-wall glass vessels, fitted with a pressure head and safety release valve, and operated behind a safety shield. Much higher pressures may be achieved using steel autoclaves. * Carbonylative Coupling Reactions: Synthesis of Carbonyl DerivativesCan we intercept the acyl intermediate with a main-group organometallic, or other carbon nucleophile? This could be a useful synthesis of ketones (Scheme 4.2). 3 How would the mechanism work? It would require coordination and insertion of CO before reductive elimination (Scheme 4.3). As reductive elimination is usually fast, CO must be involved before transmetallation. Ketone production will be favoured over direct coupling if the rate of CO insertion is faster than the rate of transmetallation of L 2 PdR'X. We can make CO chemistry faster by increasing the pressure; we can make transmetallation slower by using a less-reactive organometallic, and also by slow addition, to get the right kinetics. Although slow transmetallation is favoured by the use of less electropositive metals, M, such as tin, boron and silicon, a wide range of organometallics have been employed too. In addition to tin (Schemes 4.4 and 4.5) 4,5 , boron (Scheme 4.6) 6 and silicon (Scheme 4.7), 7 examples include aluminium (Scheme 4.8) 8 and zinc (Scheme 4.9) 9 . * WARNING Carbon monoxide is highly toxic. All reactions using this gas should be carried out in an efficient fume cupboard. Reactions under pressure should be carried out behind additional safety shielding.

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New synthesis of nitrogen heterocycles through amide-directed hydrocarbonylation of alkenamides catalyzed by rhodium complexes

Cited by 66 publications

References 0 publications

Pd-Catalyzed Cross-Coupling of Potassium Alkenyltrifluoroborates with 2-Chloroacetates and 2-Chloroacetamides

Pd-Catalyzed Cross-Coupling of Potassium Alkenyltrifluoroborates with 2-Chloroacetates and 2-Chloroacetamides

Heterocyclization of amides of alkenylcarboxylic acids

Carbonylation

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