Oxidative Rearrangement of Primary Amines Using PhI(OAc)2 and Cs2CO3

Yamakoshi, Wataru; Arisawa, Mitsuhiro; Murai, Kenichi

doi:10.1021/acs.orglett.9b00559

Cited by 24 publications

(18 citation statements)

References 30 publications

(17 reference statements)

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“…Similarly, product 6aa was also formed in an 84% yield from the reaction of 3a with PIDA in methanol in the presence of TEMPO (Scheme c). The results from radical-scavenger experiments ruled out the involvement of the radical pathway, which is in stark contrast to what is observed by Murai and co-workers in the PIDA-mediated direct 1,2-C-to-N migration of amines . Based on these results and effects of substituents on the C-2 aryl ring on the yields of products, we believe that the reaction involves a non-radical, ionic mechanism.…”

Section: Results and Discussioncontrasting

confidence: 73%

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Phenyliodine(III) Diacetate-Mediated 1,2-ipso-Migration in Mannich Bases of Imidazo[1,2-a]pyridines: Preparation of N-Acetoxymethyl/Alkoxymethyl-N-arylimidazo[1,2-a]pyridine-3-amines

et al. 2020

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Phenyliodine(III) diacetate -mediated 1,2-ipso-migration of an imidazo[1,2-a]pyridine ring via the formation of an aziridine intermediate in Mannich bases derived from imidazo[1,2-a]pyridines, 2-pyridylamines or arylamines, and formaldehyde is reported. The imidazo[1,2-a]pyridines bearing different substituents showed excellent migratory aptitude and resulted in corresponding N-acetoxymethyl-, N-alkoxymethyl-, and N-hydroxymethyl-N-arylimidazo[1,2-a]pyridine-3-amine derivatives in moderate to excellent (42 examples; 35−93%) yields. Radical trapping experiments confirmed the involvement of a non-radical intermediate. The developed protocol is amenable for a scale-up reaction, and synthetic utility of N-acetoxymethyl products was demonstrated by transforming them to corresponding N-(pyridin-2-yl)imidazo[1,2-a]pyridin-3-amines.

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Section: Results and Discussioncontrasting

confidence: 73%

“…However, Zhu and co-workers failed to isolate the N -(alkoxymethyl)- N -arylpyridin-2-amine intermediate in hexafluoroisopropanol (HFIP). Murai and co-workers reported phenyliodine(III) diacetate (PIDA)-mediated oxidative rearrangement of primary and secondary amines via 1,2-C-to-N migration of amines (Scheme d) …”

Section: Introductionmentioning

confidence: 99%

Phenyliodine(III) Diacetate-Mediated 1,2-ipso-Migration in Mannich Bases of Imidazo[1,2-a]pyridines: Preparation of N-Acetoxymethyl/Alkoxymethyl-N-arylimidazo[1,2-a]pyridine-3-amines

et al. 2020

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“…13 4-Chloro-N-cyclohexylaniline (4t). 44 Column chromatography (petroleum ether/CH 2 Cl 2 = 100:1 to 30:1; silica gel, 100−200 mesh); white solid (38.9 mg, 93% yield). 1…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Light-Promoted Low-Valent-Tungsten-Catalyzed Ambient Temperature Amination of Boronic Acids with Nitroaromatics

et al. 2022

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Triggering C−N bond formation with nitroaromatics and boronic acids at mild conditions is highly desirable, since most prior works were carried out under harsh conditions and sometimes suffered from poor chemo-or regioselectivity. Herein, a low-valent-tungsten-catalyzed reaction that enables the ambient temperature amination of boronic acids with nitroaromatics is disclosed. With readily available W(CO) 6 as a precatalyst under external-photosensitizer-free conditions, nitroaromatics smoothly undergo C−N coupling reactions with their boronic acid partners, delivering structurally diverse secondary amines in good yields (>50 examples, yields up to 96%). This methodology is both scalable and highly chemoselective and engages both aliphatic and aromatic boronic acid partners. The catalysis is initiated by the deoxygenation of nitroaromatics by a trans-[W(CO) 4 (PPh 3 ) 2 ] (trans-W, PPh 3 = triphenylphosphine) complex, which forms in situ via ligand replacement.

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“…This method enabled facile synthesis of cyclic amines such as benzoazepine 261 (n = 1) and benzosuberan 261 (n = 2) in significant yields (Scheme 69). 101 Substituents such as chloro, methoxy, ester and trifluoromethyl groups were well tolerated. Scheme 69.…”

Section: Synthesis Of Bicyclic Heterocyclesmentioning

confidence: 99%

Hypervalent iodine-mediated synthesis and late-stage functionalization of heterocycles

Shetgaonkar¹,

Singh²

2021

Arkivoc

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Hypervalent iodine chemistry has witnessed exponential growth in organic synthesis in recent times. Because of the electrophilic and good-leaving nature of hypervalent iodine reagents, they react with different nucleophiles in various synthetic transformations such as rearrangements, α-functionalization of carbonyl compounds, alkene difunctionalization and oxidation reactions. Importantly, the application of hypervalent iodine reagents in the construction of heterocycles is of great interest and has been well studied over the years. This review article highlights the recent developments accomplished by hypervalent iodine reagents in the synthesis and functionalization of heterocyclic compounds.

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Oxidative Rearrangement of Primary Amines Using PhI(OAc)₂ and Cs₂CO₃

Cited by 24 publications

References 30 publications

Phenyliodine(III) Diacetate-Mediated 1,2-ipso-Migration in Mannich Bases of Imidazo[1,2-a]pyridines: Preparation of N-Acetoxymethyl/Alkoxymethyl-N-arylimidazo[1,2-a]pyridine-3-amines

Phenyliodine(III) Diacetate-Mediated 1,2-ipso-Migration in Mannich Bases of Imidazo[1,2-a]pyridines: Preparation of N-Acetoxymethyl/Alkoxymethyl-N-arylimidazo[1,2-a]pyridine-3-amines

Light-Promoted Low-Valent-Tungsten-Catalyzed Ambient Temperature Amination of Boronic Acids with Nitroaromatics

Hypervalent iodine-mediated synthesis and late-stage functionalization of heterocycles

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