- Synthesis and density functional theory studies of azirinyl and oxiranyl functionalized isoindigo and (3Z,3′Z)-3,3′-(ethane-1,2-diylidene)bis(indolin-2-one) derivatives
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The design and synthesis of functionalized isoindigo compounds by reaction of isoindigo with (S)-glycidyl tosylate, epibromohydrin, 2-(bromomethyl)-1-(arylsulfonyl)aziridine, and 2-(bromomethyl)-1-(alkylsulfonyl)aziridine in the presence of MeONa proceed under mild conditions in moderate yields. (3Z,3′Z)-3,3′-(Ethane-1,2-diylidene)bis(1-(oxiran-2-ylmethyl)indolin-2-one), with an extended central olefin π-conjugated moiety was also reacted with methyl-oxiranes to give the corresponding N.N″-disubstituted derivative. Calculations with DFT and TD-DFT of hypothetical isoindigo-thiophene DA molecules with various electron withdrawing substituents, including aziridine, oxirane, nitrile, carbonyl, and sulfonate, indicated that the proximity and strength of the functional group have a significant effect on the HOMO, LUMO, vertical excitation energy and oscillator strength of the π-π? transitions.
- Khalili, Gholamhossein,McCosker, Patrick M.,Clark, Timothy,Keller, Paul A.
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- Ring opening of 2-(bromomethyl)-1-sulfonylaziridines towards 1,3-heteroatom substituted 2-aminopropane derivatives
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1,3-Heteroatom substituted 2-aminopropane derivatives have been prepared from 2-(bromomethyl)-1-sulfonylaziridines for the first time using sodium azide or different potassium phenoxides in water in the presence of silica gel. The applicability of 1-arenesulfonyl-2-(bromomethyl)aziridines for the synthesis of functionalized sulfonamides has also been demonstrated towards different 1,3-dialkoxy-2-(tosylamino)propanes and 1,3-dialkylthio-2-(tosylamino)propanes upon treatment with the appropriate sodium alkoxide or sodium alkylthiolate in the corresponding alcohol or in methanol, respectively.
- D'hooghe, Matthias,Rottiers, Mario,Kerkaert, Inge,De Kimpe, Norbert
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- Twofold Radical-Based Synthesis of N, C-Difunctionalized Bicyclo[1.1.1]pentanes
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Bicyclo[1.1.1]pentylamines (BCPAs) are of growing importance to the pharmaceutical industry as sp3-rich bioisosteres of anilines and N-tert-butyl groups. Here we report a facile synthesis of 1,3-disubstituted BCPAs using a twofold radical functionalization strategy. Sulfonamidyl radicals, generated through fragmentation of α-iodoaziridines, undergo initial addition to [1.1.1]propellane to afford iodo-BCPAs; the newly formed C-I bond in these products is then functionalized via a silyl-mediated Giese reaction. This chemistry also translates smoothly to 1,3-disubstituted iodo-BCPs. A wide variety of radical acceptors and iodo-BCPAs are accommodated, providing straightforward access to an array of valuable aniline-like isosteres.
- Anderson, Edward A.,Mousseau, James. J.,Nugent, Jeremy,Owen, Benjamin,Pickford, Helena D.,Smith, Russell C.
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p. 9729 - 9736
(2021/07/19)
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- Aziridination of Olefins
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A process for aziridination of olefins using NaIO4/alkali metal bromide/H+/Chloramine-T combination in presence of dipolar aprotic solvent under ambient conditions to obtain aziridines is disclosed.
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Page/Page column 4-6
(2012/09/05)
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- Reactivity of activated versus nonactivated 2-(bromomethyl)aziridines with respect to sodium methoxide: A combined computational and experimental study
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The difference in reactivity between the activated 2-bromomethyl-1- tosylaziridine and the nonactivated 1-benzyl-2-(bromomethyl)aziridine with respect to sodium methoxide was analyzed by means of DFT calculations within the supermolecule approach, taking into account explicit solvent molecules. In addition, the reactivity of epibromohydrin with regard to sodium methoxide was assessed as well. The barriers for direct displacement of bromide by methoxide in methanol are comparable for all three heterocyclic species under study. However, ring opening was found to be only feasible for the epoxide and the activated aziridine, and not for the nonactivated aziridine. According to these computational analyses, the synthesis of chiral 2-substituted 1-tosylaziridines can take place with inversion (through ring opening/ring closure) or retention (through direct bromide displacement) of configuration upon treatment of the corresponding 2-(bromomethyl)aziridines with 1 equiv of a nucleophile, whereas chiral 2-substituted 1-benzylaziridines are selectively obtained with retention of configuration (via direct bromide displacement). Furthermore, the computational results showed that explicit accounting for solvent molecules is required to describe the free energy profile correctly. To verify the computational findings experimentally, chiral 1-benzyl-2-(bromomethyl)aziridines and 2-bromomethyl-1-tosylaziridines were treated with sodium methoxide in methanol. The presented work concerning the reactivity of 2-bromomethyl-1- tosylaziridine stands in contrast to the behavior of the corresponding 1-tosyl-2-(tosyloxymethyl)aziridine with respect to nucleophiles, which undergoes a clean ring-opening/ring-closure process with inversion of configuration at the asymmetric aziridine carbon atom.
- Goossens, Hannelore,Vervisch, Karel,Catak, Saron,Stankovic, Sonja,D'Hooghe, Matthias,De Proft, Frank,Geerlings, Paul,De Kimpe, Norbert,Waroquier, Michel,Van Speybroeck, Veronique
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scheme or table
p. 8698 - 8709
(2012/01/05)
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- NaIO4/LiBr-mediated aziridination of olefins using chloramine-T
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A new milder protocol for aziridination of a variety of olefins has been described. The process employs catalytic amount of sodium metaperiodate (NaIO4) as an oxidant and LiBr and chloramine-T as the bromine and nitrogen sources, respectively. Interestingly, the formation of aziridine products in all the cases studied takes place presumably through a process of 1,2-aminobromination of alkenes.
- Karabal, Pratibha U.,Chouthaiwale, Pandurang V.,Shaikh, Tanveer M.,Suryavanshi, Gurunath,Sudalai, Arumugam
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experimental part
p. 6460 - 6462
(2011/01/03)
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- Regio- and stereocontrolled synthesis of novel 3-sulfonamido-2,3,4,5- tetrahydro-1,5-benzothiazepines from 2-(bromomethyl)- or 2-(sulfonyloxymethyl) aziridines
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2-(Bromomethyl)-1-sulfonylaziridines were converted into novel 3-sulfonamido-2,3,4,5-tetrahydro-1,5-benzothiazepines upon treatment with 2-aminothiophenol in THF in the presence of K2CO3. Starting from 3-substituted 2-(sulfonyloxymet
- Karikomi, Michinori,D'Hooghe, Matthias,Verniest, Guido,De Kimpe, Norbert
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scheme or table
p. 1902 - 1904
(2009/01/31)
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- Ring opening reactions of 1-arenesulfonyl-2-(bromomethyl)aziridines
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The reactivity of 1-arenesulfonyl-2-(bromomethyl)aziridines with respect to lithium dialkylcyanocuprates and lithium dialkylcuprates (Gilman reagents) has been evaluated for the first time, pointing to the conclusion that these substrates can be applied successfully as synthetic equivalents for the 2-aminopropane dication synthon towards 2-alkylaziridines and α-branched N-tosylamides in good yields.
- D'Hooghe, Matthias,Kerkaert, Inge,Rottiers, Mario,De Kimpe, Norbert
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p. 3637 - 3641
(2007/10/03)
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- N-bromoamides as versatile catalysts for aziridination of olefins using chloramine-T
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N-Bromoamides catalyze effectively the aziridination of electron-deficient as well as electron-rich olefins using chloramine-T (N-chloro-N-sodio-p-toluenesulfonamide) as a nitrogen source under ambient conditions to afford the corresponding aziridines in
- Thakur, Vinay V.,Sudalai
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p. 989 - 992
(2007/10/03)
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- Electron transfer induced ring opening of 2-(bromomethyl)aziridines by magnesium in methanol
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Magnesium metal in methanol was used as a simple electron transfer induced ring-opening reagent of 2-(bromomethyl)aziridines to afford allylamines derivatives in 70-90% yield.
- Tehrani, Kourosch Abbaspour,NguyenVan, Tuyen,Karikomi, Michinori,Rottiers, Mario,De Kimpe, Norbert
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p. 7145 - 7152
(2007/10/03)
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- Pyridinium hydrobromide perbromide: A versatile catalyst for aziridination of olefins using chloramine-T
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Formula presented Pyridinium hydrobromide perbromide (PyHBr3) catalyzes effectively the aziridination of electron-deficient as well as electron-rich olefins using Chloramine-T (N-chloro-N-sodio-p-toluenesulfonamide) as a nitrogen source to afford the corr
- Ali, Sayyed Iliyas,Nikalje, Milind D.,Sudalai
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p. 705 - 707
(2008/02/12)
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