<i>m</i>‐CPBA‐Mediated IntramolecularAminohydroxylation of <i>N</i>‐Sulfonyl Aminoalkenes to Synthesize β‐Hydroxyl Cyclic Amines

Yin, Yan; Zhou, Hong; Sun, Guodong; Liu, Xichen

doi:10.1002/jhet.2169

Cited by 9 publications

(3 citation statements)

References 35 publications

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“…Reaction of ( E )-4-methyl- N -(4-phenylbut-3-en-1-yl)benzenesulfonamide 8a (25 mg, 0.08 mmol) and malonoyl peroxide 1 (16 mg, 0.12 mmol) in HFIP (0.2 mL) according to General Procedure 3 followed by hydrolysis in 1 M NaOH/THF (0.8 mL, 1:1) gave the crude alcohol (1:13 cis / trans ). Purification by silica gel flash column chromatography (hexane/EtOAc 4:6) gave title compound 9a (18 mg, 0.06 mmol, 71%) as a white solid: mp 148–149 °C (lit . 155–156 °C); IR (ATR)/cm –1 3474, 3065, 3034, 2929, 2892; 1 H NMR (500 MHz, CDCl 3 ) δ 7.75 (d, J = 8.1 Hz, 2H), 7.34–7.33 (m, 4H), 7.31 (d, J = 8.1 Hz, 2H), 7.28–7.26 (m, 1H), 4.66 (bs, 1H), 4.18 (bs, 1H), 3.73 (td, J = 9.4, 2.1 Hz, 1H), 3.53 (td, J = 9.9, 7.0 Hz, 1H), 2.43 (s, 3H), 2.07–2.00 (m, 1H), 1.77–1.73 (m, 1H), 1.37–1.38 (m, 1H); 13 C NMR (126 MHz, CDCl 3 ) δ 143.7, 139.9, 134.7, 129.7, 128.7, 128.9, 127.7, 126.3, 79.1, 72.0, 46.8, 31.5, 21.7; LRMS (ES + APCI) m / z 318.0 [M + H] + .…”

Section: Experimental Sectionmentioning

confidence: 99%

Alkene Oxyamination Using Malonoyl Peroxides: Preparation of Pyrrolidines and Isoxazolidines

et al. 2018

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Treatment of homoallylic N-tosyl amines or allylic N-tosyl hydroxylamines with 1.5 equiv of a malonoyl peroxide provides a stereoselective method to access functionalized pyrrolidines and isoxazolidines. This metal free alkene oxyamination proceeds in 50-85% yield and up to 13:1 trans-selectivity. In addition, the relative stereochemistry of the oxygen and nitrogen substituents can be inverted through an oxidation/reduction sequence or inverting the stereochemistry of the starting alkene. Mechanistic investigations show a higher reactivity for hydroxyl nucleophiles over sulfonamide nucleophiles revealing a preference for dioxygenation over oxyamination.

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Section: Experimental Sectionmentioning

confidence: 99%

Alkene Oxyamination Using Malonoyl Peroxides: Preparation of Pyrrolidines and Isoxazolidines

et al. 2018

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“…In addition, the hydroxylation product 3a″ was isolated in 34% yield. This compound originated from a side reaction of the unsaturated amide 1a with m CPBA . No diamination product was detected, even though this is the major product resulting from copper-catalyzed cyclization reactions .…”

Section: Resultsmentioning

confidence: 95%

Iodoarene-Catalyzed Oxyamination of Unactivated Alkenes to Synthesize 5-Imino-2-Tetrahydrofuranyl Methanamine Derivatives

et al. 2020

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Reported here is the room-temperature metal-free iodoarene-catalyzed oxyamination of unactivated alkenes. In this process, the alkenes are difunctionalized by the oxygen atom of the amide group and the nitrogen in an exogenous HNTs 2 molecule. This mild and open-air reaction provided an efficient synthesis to N-bistosylsubstituted 5-imino-2-tetrahydrofuranyl methanamine derivatives, which are important motifs in drug development and biological studies. Mechanistic study based on experiments and density functional theory calculations showed that this transformation proceeds via activation of the substrate alkene by an in situ generated cationic iodonium(III) intermediate, which is subsequently attacked by an oxygen atom (instead of nitrogen) of amides to form a fivemembered ring intermediate. Finally, this intermediate undergoes an S N 2 reaction by NTs 2 as the nucleophile to give the oxygen and nitrogen difunctionalized 5-imino-2-tetrahydrofuranyl methanamine product. An asymmetric variant of the present alkene oxyamination using chiral iodoarenes as catalysts also gave promising results for some of the substrates.

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“…With this in mind, we became interested in using intramolecular aminohydroxylation to construct a functionalized pyrrolidine derivative, which would then act as a precursor to the PBTDs or PBDs. Intramolecular aminohydroxylation of alkenes is an area of recent interest in heterocyclic synthesis and has been used to access simple prolinol derivatives. − Using this, our initial hypothesis (Figure ) was that the N -(pent-4-en-1-yl)azidobenzenesulfonamide 5 and N -(pent-4-en-1-yl)azidobenzamide 6 would undergo aminohydroxylation to yield N -arylazido-substituted prolinols 7 and 8 , respectively, which could then be used to synthesize PBDs and PBTDs.…”

Section: Introductionmentioning

confidence: 99%

N-Alkylation and Aminohydroxylation of 2-Azidobenzenesulfonamide Gives a Pyrrolobenzothiadiazepine Precursor Whereas Attempted N-Alkylation of 2-Azidobenzamide Gives Benzotriazinones and Quinazolinones

et al. 2017

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N-Alkylation of 2-azidobenzenesulfonamide with 5-bromopent-1-ene gave an N -pentenyl sulfonamide, which underwent intramolecular aminohydroxylation to give an N -(2-azidoaryl)sulfonyl prolinol, a precursor for the synthesis of a pyrrolobenzothiadiazepine. The attempted N-alkylation of 2-azidobenzamide gave a separable mixture (∼1:1) of a benzotriazinone and a quinazolinone in a 72% combined yield. Other primary alkyl halides (3 examples) gave similar mixtures of benzotriazinones and quinazolinones. Benzylic, allylic, and secondary and tertiary alkyl halides (5 examples) gave only benzotriazinones in moderate yields. The results of mechanistic studies show the likely involvement of nitrene intermediates in the quinazolinone pathway and a second pathway involving a dimethylsulfoxide or dimethylsulfide-mediated conversion of 2-azidobenzamide into benzotriazinones.

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m‐CPBA‐Mediated IntramolecularAminohydroxylation of N‐Sulfonyl Aminoalkenes to Synthesize β‐Hydroxyl Cyclic Amines

Cited by 9 publications

References 35 publications

Alkene Oxyamination Using Malonoyl Peroxides: Preparation of Pyrrolidines and Isoxazolidines

Alkene Oxyamination Using Malonoyl Peroxides: Preparation of Pyrrolidines and Isoxazolidines

Iodoarene-Catalyzed Oxyamination of Unactivated Alkenes to Synthesize 5-Imino-2-Tetrahydrofuranyl Methanamine Derivatives

N-Alkylation and Aminohydroxylation of 2-Azidobenzenesulfonamide Gives a Pyrrolobenzothiadiazepine Precursor Whereas Attempted N-Alkylation of 2-Azidobenzamide Gives Benzotriazinones and Quinazolinones

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