Brønsted Base-Modulated Regioselective Pd-Catalyzed Intramolecular Aerobic Oxidative Amination of Alkenes: Formation of Seven-Membered Amides and Evidence for Allylic C−H Activation

Wu, Liang; Qiu, Shuifa; Liu, Guosheng

doi:10.1021/ol900941t

Cited by 117 publications

(38 citation statements)

References 39 publications

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“…Although significant developments in aza-Wacker-type reactions have been achieved, the existing aza-Wacker process generally requires non-basic nitrogen nucleophiles such as carboxamides, carbamates, and sulfonamides as amination reagents, under relatively high oxygen pressures (4-10 atm.) or in the presence of an external oxidant source such as benzoquinone (BQ), PhBQ, PhI(OAc) 2 , or PhI(OPiv) 2 [19][20][21][22][23][24][25][26][27][28][29][30][31][32][33]. In contrast, the oxidative amination of olefins using more basic, simple amines as substrates has been less explored, and is generally limited to intramolecular reactions [34][35][36][37][38], because of the strong coordination of amines to Pd, which results in catalyst deactivation.…”

Section: Open Accessmentioning

confidence: 99%

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Palladium-Catalyzed Intermolecular Oxidative Amination of Alkenes with Amines, Using Molecular Oxygen as Terminal Oxidant

Obora

Ishii

2013

Catalysts

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Abstract:In this review, we summarize recent progress from our group with regard to Pd-catalyzed oxidative amination of alkenes with amines. Intermolecular oxidative amination of alkenes with secondary anilines was induced using a palladium-complex catalyst combined with molybdovanadophosphate as a co-catalyst under dioxygen, leading to allylic amines and enamines in good yields with high selectivities. The reaction proceeded efficiently, using molecular oxygen as the terminal oxidant. In addition, palladium-catalyzed oxidative amination of alkenes with anilines as primary amines was achieved using molecular oxygen as the sole oxidant, producing (Z)-N-alkenyl-substituted anilines in high yields.

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Section: Open Accessmentioning

confidence: 99%

“…Pd(II)-catalyzed oxidative allylic amination by selective allylic C-H bond functionalization of alkenes with amines is an alternative efficient methodology for preparing nitrogen-containing unsaturated compounds [25,42,43]. However, there has been limited work on reactions using non-substituted simple alkenes.…”

Section: Open Accessmentioning

confidence: 99%

Palladium-Catalyzed Intermolecular Oxidative Amination of Alkenes with Amines, Using Molecular Oxygen as Terminal Oxidant

Obora

Ishii

2013

Catalysts

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“…8e, 16 Unfortunately, however, all attempts to cyclize 18 under Pd catalysis, Scheme 1 General retrosynthetic analysis of the natural products 5. Target heterocycles 6 and 6a as advanced key intermediates.…”

Section: Resultsmentioning

confidence: 99%

“…IR (KBr, ν): 2928(KBr, ν): , 2369(KBr, ν): , 1630(KBr, ν): , 1607(KBr, ν): , 1508(KBr, ν): , 1356(KBr, ν): , 1281(KBr, ν): , 1244 (14) and 71 (18). HRMS m/z calcd for C 16 Method B: a magnetically stirred mixture of compound 26 (24 mg, 0.055 mmol) and 10% Pd/C (1 mg) in anhydrous MeOH (2 mL) was exposed to a hydrogen atmosphere (1 atm. ) for 2 h at room temperature.…”

Section: Apparatusmentioning

confidence: 99%

A convenient approach to an advanced intermediate toward the naturally occurring, bioactive 6-substituted 5-hydroxy-4-aryl-1H-quinolin-2-ones

Larghi

Kaufman

2016

Org. Biomol. Chem.

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5-Hydroxy-4-aryl-3,4-dihydro-1H-quinolin-2-ones are a small family of natural products isolated from fungal strains of Penicillium and Aspergillus. Most of its members, which are insecticides and anthelmintics, carry an isoprenoid C-6 side chain. The synthesis of a 6-propenyl-substituted advanced intermediate for the total synthesis of these natural products is presented in this paper. This was achieved through the stereoselective construction of a β,β-diarylacrylate derivative from 6-nitrosalicylaldehyde, using a Wittig olefination and a Heck-Matsuda arylation, followed by a selective Fe 0 -mediated reductive cyclization.Installation of the 6-propenyl side chain was performed by 5-O-allylation of the heterocycle, followed by Claisen rearrangement and conjugative migration of the allyl double bond, as the key steps. The Grubbs II-catalyzed olefin cross metathesis of the 6-allyl moiety with 2-methylbut-2-ene to afford a precursor of peniprequinolone is also reported.

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“…Pd-каталізоване внутрішньомолекулярне окис-нювальне амінування ненасичених амідів 207 при дії основи Бренстеда приводить до азепінону 208 [104] (схема 87). Регіоспецифічний синтез 7-ендо-лактаму 210 був здійснений в умовах Pd-каталізованого йоду-вання ненасичених амідів 209 із атомом гало-гену в δ-положенні до амідної функції [105] (схе-ма 88).…”

Section: синтез 7-та 8-членних лактамівunclassified

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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Brønsted Base-Modulated Regioselective Pd-Catalyzed Intramolecular Aerobic Oxidative Amination of Alkenes: Formation of Seven-Membered Amides and Evidence for Allylic C−H Activation

Cited by 117 publications

References 39 publications

Palladium-Catalyzed Intermolecular Oxidative Amination of Alkenes with Amines, Using Molecular Oxygen as Terminal Oxidant

Palladium-Catalyzed Intermolecular Oxidative Amination of Alkenes with Amines, Using Molecular Oxygen as Terminal Oxidant

A convenient approach to an advanced intermediate toward the naturally occurring, bioactive 6-substituted 5-hydroxy-4-aryl-1H-quinolin-2-ones

Heterocyclization of amides of alkenylcarboxylic acids

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