Palladium‐Catalyzed 2‐(Neopentylsulfinyl)aniline Directed C–H Acetoxylation and Alkenylation of Arylacetamides

Barysevich, Maryia V.; Laktsevich-Iskryk, Marharyta V.; Krech, Anastasiya V.; Жабинский, В. Н.; Хрипач, В. А.; Hurski, Alaksiej L.

doi:10.1002/ejoc.201901646

Cited by 8 publications

(7 citation statements)

References 84 publications

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“…Hurski and co-workers recently reported that, after the Pd-catalyzed ring opening of cyclopropyl alcohols ( 31 ) and generation of enones ( 32 ), these intermediates can be used as alkenylating reagents (Scheme ). Thus, arenes bearing a 2-(neopentylsulfinyl)aniline directing group can undergo Pd-catalyzed C–H activation to synthesize the alkenylated arene ( 33 ) in good yields. This protocol is compatible with a number of functional groups, like alcohols ( 33a ) and nitroarenes ( 33b ).…”

Section: Metal-catalyzed β-Carbon Elimination (Metal Homoenolates)mentioning

confidence: 99%

Selective Carbon–Carbon Bond Cleavage of Cyclopropanols

et al. 2020

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The carbon–carbon (C–C) bond cleavage of cyclopropanols is a wide area of research with much current activity. This review highlights new developments in this area over the past two decades. A summary is made of the three main reactivity modes, namely, homoenolate chemistry, β-keto radical chemistry, and acid-catalyzed ring-opening, as well as all other methods for the C–C bond cleavage and functionalization of cyclopropanols, including base-mediated ring-opening, metal-catalyzed C–C insertions and eliminations, oxidative fragmentation using hypervalent iodine reagents, reactions of donor–acceptor cyclopropanols, and pericylic reactions. Emphasis is placed on the synthetic utility of cyclopropanols and related derivatives, which have emerged as unique three-carbon synthons.

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Section: Metal-catalyzed β-Carbon Elimination (Metal Homoenolates)mentioning

confidence: 99%

Selective Carbon–Carbon Bond Cleavage of Cyclopropanols

et al. 2020

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“…An additional arylation protocol was also reported by the same group, where the enones generated from the ring opening of cyclopropanols were used as alkenylation agents. 10…”

Section: Manmohan Kapurmentioning

confidence: 99%

Strained cycloalkanols in C–C bond formation reactions: a boon in disguise!

Jha¹,

Mishra²,

Kapur³

2023

Org. Chem. Front.

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“…13 The crude product was purified by flash column chromatography on silica gel (1→2% EtOAc/PE) to provide a colorless oil (51.6 mg, 0.195 mmol, 78% yield); 1 H NMR (500 MHz, CDCl 3 ) δ 7.34 -7.24 (m, 6H), 7.19 (t, J = 7.4 Hz, 4H), 6.39 (d, J = 15.9 Hz, 1H), 6.17 (dt, J = 15.9, 6.9 Hz, 1H), 2.92 (t, J = 7.6 Hz, 2H), 2.76 (t, J = 7. 6…”

Section: -(4-methoxyphenyl)-1-phenylhexan-3-one (13j)mentioning

confidence: 99%

“…phenyldecan-3-one (14b): Obtained according to the general procedure B from cyclopropanol 11а and 2-bromohex-1-ene. The crude product was purified by flash column chromatography on silica gel (1→1.5% EtOAc/PE) to provide a colorless oil (33 6. mg, 0.137 mmol, 55% yield); 1 H NMR (500 MHz, CDCl 3 ) δ 7.31 -7.25 (m, 2H), 7.22 -7.17 (m, 3H), 4.72 (s, 1H), 4.65 (s, 1H), 2.93 -2.88 (m, 2H), 2.78 -2.73 (m, 2H), 2.56 -2.50 (m, 2H), 2.31 -2.24 (m, 2H), 2.03 -1.97 (m, 2H), 1.43 -1.36 (m, 2H), 1.35 -1.25 (m, 2H), 0.90 (t, J = 7.3 Hz, 3H).…”

mentioning

confidence: 99%

Ti(OiPr)₄-Enabled Dual Photoredox and Nickel-Catalyzed Arylation and Alkenylation of Cyclopropanols

et al. 2021

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Readily available from esters and kektones, cyclopropanols are inclined to undergo diverse ring-opening reactions. Their one-electron oxidation is a conventional way to β-carbonyl radicals. However, despite this fact, their application as a coupling partner in dual photoredox and nickel-catalyzed reactions with organic halides remains underdeveloped. Here, we report that Ti(OiPr)4 additive enables this elusive cross-coupling with aryl and alkenyl bromides affording βsubstituted ketones. 2Nickel-catalyzed coupling of the photochemically generated alkyl radicals 1 with aryl, alkenyl or alkyl halides has recently emerged as a powerful tool for the C-C bond construction (Scheme 1A). 2 Proceeding under mild conditions, these reactions generally tolerate sensitive functional groups and moreover, can be deployed for the formation of an asymmetric setereocenter. 3 The scope of the radical precursors used in the coupling is exceptionally broad. After the pioneering reports on the arylation of organotrifluoroborates, aliphatic carboxylic acids and N,N-dimethylaniline by Molander 4 and MacMillan and Doyle, 5 various alternative coupling partners were utilized including alkylsylicates, 6 monoalkyl oxalates, 7 dihydropyridines, 8 , 9 alkyl halides, 10 alkanes, 11 oxiranes, 12 aziridines, 13 cycloalkanone oxyme-carboxylates, 14 N-hydroxyphthalimide esters, 15 Katritzky salts, 16 alkylsulfinate salts, 17 xanthate esters, 18 boracene-based alkyl borates, 19 linear 20 and cyclic alcohols. 21 Being a source of β-ketoradicals 3, 22 cyclopropanols 1 can also undergo the photoredox/nickel dual catalyzed reaction to provide β-substituted ketones (Scheme 1B). 21 However, scope of cyclopropanols that can be engaged in this coupling is rather narrow. Shenvi reported arylation and alkenylation of tricyclic silyloxycyclopropanes 4 promoted by an iridium photocatalyst and a nickel complex. 21a One of the obtained β-substituted ketones 5 was further efficiently applied in a concise synthesis of natural alkaloid GB-22. 21a Another example of the photoredox initiated ring-opening arylation was described by Rueping. 21b The presence of PMP group in 6 was crucial because the formation of alkoxy radical 2 was initiated by the one-electron oxidation of this moiety. Here, we report that limitations in the scope of photoredox and nickel dual-catalyzed cyclopropanol arylation and alkenylation can be overcome when the reaction is carried out in the presence of Ti(OiPr)4 as an additive. Under these conditions, β-substituted ketones 10 can be obtained from cyclopropanols 8 and aryl-or vinyl-bromides 9. cyclopropanols when carried out in the presence of Ti(OiPr)4 additive. The cross-coupling is compatible with functional groups including unprotected hydroxyl and proceeds under conditions mild enough for the preparation of enantiomerically pure ketones bearing a sensitive αstereocenter.ASSOCIATED CONTENT Supporting Information.

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Palladium‐Catalyzed 2‐(Neopentylsulfinyl)aniline Directed C–H Acetoxylation and Alkenylation of Arylacetamides

Cited by 8 publications

References 84 publications

Selective Carbon–Carbon Bond Cleavage of Cyclopropanols

Selective Carbon–Carbon Bond Cleavage of Cyclopropanols

Strained cycloalkanols in C–C bond formation reactions: a boon in disguise!

Ti(OiPr)₄-Enabled Dual Photoredox and Nickel-Catalyzed Arylation and Alkenylation of Cyclopropanols

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Palladium‐Catalyzed 2‐(Neopentylsulfinyl)aniline Directed C–H Acetoxylation and Alkenylation of Arylacetamides

Cited by 8 publications

References 84 publications

Selective Carbon–Carbon Bond Cleavage of Cyclopropanols

Selective Carbon–Carbon Bond Cleavage of Cyclopropanols

Strained cycloalkanols in C–C bond formation reactions: a boon in disguise!

Ti(OiPr)4-Enabled Dual Photoredox and Nickel-Catalyzed Arylation and Alkenylation of Cyclopropanols

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Ti(OiPr)₄-Enabled Dual Photoredox and Nickel-Catalyzed Arylation and Alkenylation of Cyclopropanols