Alkene Oxyamination Using Malonoyl Peroxides: Preparation of Pyrrolidines and Isoxazolidines

Alamillo‐Ferrer, Carla; Curle, Jonathan M.; Davidson, Stuart C.; Lucas, Simon; Atkinson, Sophie; Campbell, Matthew; Kennedy, Alan R.; Tomkinson, Nicholas C. O.

doi:10.1021/acs.joc.8b00392

Cited by 23 publications

(18 citation statements)

References 68 publications

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“…The organic layer was dried with MgSO 4 and concentrated, providing 2-(but-3-en-1-yl)isoindoline-1,3-dione, which was used without further purification (1.14 g, 72%). NMR data matches previously reported spectra …”

Section: Methodssupporting

confidence: 87%

Fluorofunctionalization of C═C Bonds with Selectfluor: Synthesis of β-Fluoropiperazines through a Substrate-Guided Reactivity Switch

et al. 2018

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The halofunctionalization of alkene substrates remains an essential tool for synthetic chemists. Herein, we report regioselective ammoniofluorination of unactivated alkenes through photochemical means. A one-pot transformation of the ammonium fluoride products into pharmaceutically relevant β-fluoropiperazines is highlighted. Furthermore, a substrate-guided reactivity switch is observed: certain alkenes are shown to react with the same fluorinating reagent to instead give the less-substituted fluoride. We hope that the ammoniofluorination reaction will be of utility in the area of medicinal chemistry, where nitrogen and fluorine are among the most important heteroatoms.

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Section: Methodssupporting

confidence: 87%

Fluorofunctionalization of C═C Bonds with Selectfluor: Synthesis of β-Fluoropiperazines through a Substrate-Guided Reactivity Switch

et al. 2018

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“…Preparation of Reagents: Dibenzyl diselenide (Bn 2 Se 2 ), 1 1,2-bis((S)-8-((tertbutyldimethylsilyl)oxy)-2-methoxy-5,6,7,8-tetrahydronaphthalen-1-yl)diselane ( 6), 2 (1S,1'S)diselanediylbis (7-methoxy-1,2,3,4-tetrahydronaphthalene-8,1-diyl) dibenzoate (7), 2 (S)-6-methoxy-7-((4-methoxybenzyl)selanyl)-2,2-dimethyl-2,3-dihydro-1H-inden-1-ol, 3 and benzyl tosylcarbamate ( 16) 4 were prepared according to literature procedures.…”

Section: Literature Preparationsmentioning

confidence: 99%

“…Preparation of Alkenes: (E)- prop-1-en-1-yl)benzene (4), 5 (E)-(3methylbut-1-en-1-yl)benzene (10c), 6 (Z)- (4-(benzyloxy)but-1-en-1-yl)benzene (10d), (E)-2-(4phenylbut-3-en-1-yl)isoindoline-1,3-dione (10e), 7 (E)-cinnamyl bromide (10f), 8 (E)-4-methyl-N-(E)-4-phenylbut-3-en-1-ol, 9 methyl (E)-4-phenylbut-3-enoate (10j), 10 (E)-cinnamyl picolinate (10k), 11 (E)-1- (3-(benzyloxy)prop-1-en-1-yl)-4-fluorobenzene (10l), 12 (E)-1- (3-(benzyloxy)prop-1-en-1-yl)-4-(trifluoromethyl)benzene (10m), 12 methyl (E)-4-(4-methoxy-4-oxobut-1-en-1yl)benzoate (10n), 13 (E)-3-(4-cyanophenyl)allyl acetate (10o), 14 (E)-3-(naphthalen-2-yl)prop-2en-1-ol, 15 (E)-3- (3-(benzyloxy)prop-1-en-1-yl)thiophene (10r), 16 (E)-1-bromo-2-(prop-1-en-1yl)benzene (10s), 17 methyl (E)-5-phenylpent-3-enoate (10x), 18 1-tosyl-1H-indole-3carbaldehyde, 19 2-((4-(trifluoromethyl)benzyl)sulfonyl)benzo [d]thiazole, 20 (R,E)-4-phenylbut-3en-2-ol, 21 and (S,E)-4-phenylbut-3-en-2-ol 21 were prepared according to literature procedures.…”

Section: Literature Preparationsmentioning

confidence: 99%

“…Data for S1: 1 H NMR: (500 MHz, CDCl 3 ) δ 7.02 (d, J = 8.4 Hz, 1 H, HC( 6)), 6.99 (d, J = 2.8 Hz, 1 H, HC( 9)), 6.78 (dd, J = 8.4, 2.8 Hz, 1 H, HC (7)), 4.74 (q, J = 5.7 Hz, 1 H, HC(1)), 3.80 (s, 3 H,HC(11)), 2.76 (dt,J = 16.3,5.8 Hz,1 H,HC(2)), 2.66 (ddd,J = 16.3,7.7,5.5 Hz,1 H,H'C(2)), 2.05 -1.83 (m, 3 H,HC(3,4)), 2 H,HC(3), OH).…”

Section: Preparation Of Reagents Preparation Of Nn'-carbonylbis(4-met...mentioning

confidence: 99%

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Catalytic, Enantioselective Syn-Diamination of Alkenes

Tao¹,

Gilbert²,

Denmark

2019

Preprint

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The enantioselective, vicinal diamination of alkenes represents one of the stereocontrolled additions that remains an outstanding challenge in organic synthesis. A general solution to this problem would enable the efficient and selective preparation of widely useful, enantioenriched diamines for applications in medicinal chemistry and catalysis. In this Article we describe the first enantioselective, syn-diamination of simple alkenes mediated by a chiral, enantioenriched organoselenium catalyst together with a N,N’-bistosyl urea as the bifunctional nucleophile and N-fluorocollidinium tetrafluoroborate as the stoichiometric oxidant. Diaryl, aryl-alkyl, and alkyl-alkyl olefins bearing a variety of substituents are all diaminated in consistently high enantioselectivities selectivities but variable yields. The reaction likely proceeds through a Se(II)/Se(IV) redox catalytic cycle reminiscent of the syn-dichlorination reported previously. Furthermore, the syn-stereospecificity of the transformation shows promise for highly enantioselective diaminations of alkenes with no strong steric or electronic bias.

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“…Recently we reported efficient methods for oxidative C−O coupling of β‐dicarbonyl and N‐heterocyclic compounds with diacyl peroxides, in which one of the reagents, diacyl peroxide, acts both as an O‐component and as an oxidizing agent. Cyclic diacyl peroxides firstly prepared in the 1950 s were rediscovered a few years ago, when previously practically unavailable reactions stereoselective syn‐ and anti‐dihydroxylation of alkenes, arene oxidation, alkene oxyamination, and dioxygenation, Hofmann‐Löffler‐Freytag‐type reaction, selective sulfide oxidation, peracids formation, ring opening/halogenation of cycloalkanols, and the [3+2] cycloaddition of arynes to azides were realized. High oxidative ability, cyclic structure and absence of an acidic proton attached to the peroxide group favorably differ malonyl peroxides from related oxidants – peracids and noncyclic diacyl peroxides.…”

Section: Introductionmentioning

confidence: 99%

C−O coupling of Malonyl Peroxides with Enol Ethers via [5+2] Cycloaddition: Non‐Rubottom Oxidation

et al. 2019

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Malonyl peroxides act both as oxidants and reagents for C−O coupling in reactions with methyl and silyl enol ethers. In the proposed conditions, the oxidative C−O coupling of malonyl peroxides with enol ethers selectively proceeds, bypassing the traditional Rubottom hydroxylation of enol ethers by peroxides. It was observed that the oxidative [5+2] cycloaddition of malonyl peroxides and enol ethers is the key stage of the discovered process. Oxidative C−O coupling of silyl enol ethers leads to the formation of α‐acyloxyketones with a free carboxylic acid group. A specially developed preparative one‐pot procedure transforms ketones via silyl enol ethers formation and the following coupling into α‐acyloxyketones with yields 35–88%. The acid‐catalyzed coupling with methyl enol ethers gives remarkable products while retaining the easily oxidizable enol fragment. Furthermore, these molecules contain a free carboxylic acid group, thus these nontrivial products contain two usually incompatible acid and enol ether groups.

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Alkene Oxyamination Using Malonoyl Peroxides: Preparation of Pyrrolidines and Isoxazolidines

Cited by 23 publications

References 68 publications

Fluorofunctionalization of C═C Bonds with Selectfluor: Synthesis of β-Fluoropiperazines through a Substrate-Guided Reactivity Switch

Fluorofunctionalization of C═C Bonds with Selectfluor: Synthesis of β-Fluoropiperazines through a Substrate-Guided Reactivity Switch

Catalytic, Enantioselective Syn-Diamination of Alkenes

C−O coupling of Malonyl Peroxides with Enol Ethers via [5+2] Cycloaddition: Non‐Rubottom Oxidation

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