34954-40-0Relevant articles and documents
Twofold Radical-Based Synthesis of N, C-Difunctionalized Bicyclo[1.1.1]pentanes
Anderson, Edward A.,Mousseau, James. J.,Nugent, Jeremy,Owen, Benjamin,Pickford, Helena D.,Smith, Russell C.
supporting information, p. 9729 - 9736 (2021/07/19)
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.
Harnessing Energy-Transfer in N-Centered Radical-Mediated Synthesis of Pyrrolidines
Fodran, Peter,Wallentin, Carl-Johan
supporting information, p. 3213 - 3218 (2020/06/02)
Atom transfer radical addition (ATRA), cyclization (ATRC), and polymerization (ATRP) are valuable synthetic methods for the functionalization of olefins. With the advent of photoredox catalysis, visible-light became a popular tool for the initiation of these reactions. We have developed a protocol that enables easy access to distally functionalized pyrrolidines employing blue-light mediated atom transfer radical [3+2] cyclization. The reaction is scalable, proceeds at very mild conditions. tolerates various functional groups, and provides the corresponding products in good to excellent yields. If rigid olefins are utilized as the reaction partners, the products can be isolated as single diastereomers. The mechanistic investigations provide strong support for an energy-transfer mechanism.
Visible-Light-Mediated Annulation of Electron-Rich Alkenes and Nitrogen-Centered Radicals from N-Sulfonylallylamines: Construction of Chloromethylated Pyrrolidine Derivatives
Crespin, Lorène N. S.,Greb, Andreas,Blakemore, David C.,Ley, Steven V.
, p. 13093 - 13108 (2017/12/26)
A visible-light-mediated annulation of N-sulfonylallylamines and olefins is reported. Rapid access to highly functionalized chloromethylated pyrrolidines can be achieved using mild conditions for the generation of nitrogen-centered radicals. Both a transi
Synthesis of 3-aza-bicyclo[3.1.0]hexan-2-one derivatives via gold-catalyzed oxidative cyclopropanation of N -allylynamides
Wang, Kai-Bing,Ran, Rui-Qiao,Xiu, Shi-Dong,Li, Chuan-Ying
supporting information, p. 2374 - 2377 (2013/06/27)
N-Allylynamides with various functional groups and different substitution patterns can be converted into 3-aza-bicyclo[3.1.0]hexan-2-one derivatives in moderate to high yield using IMesAuCl/AgBF4 as the catalyst and pyridine N-oxide as the oxidant. A noncarbene mediated approach is proposed as the mechanism.
Copper-catalyzed trifluoromethylation and cyclization of aromatic-sulfonyl-group-tethered alkenes for the construction of 1,2-benzothiazinane dioxide type compounds
Dong, Xiang,Sang, Rui,Wang, Qiang,Tang, Xiang-Ying,Shi, Min
supporting information, p. 16910 - 16915 (2014/01/06)
A multi-talented system: An efficient copper-catalyzed tandem trifluoromethylation/annulation of an electron-deficient aromatic ring has been developed. This method provides a powerful and straightforward way to synthesize trifluoromethylated 1,2-benzothiazinane dioxides under mild conditions (see scheme). The mechanism was investigated by a series of kinetic experiments and isotopic labeling studies.
Gold(l)-Catalyzed amination of allylic alcohols with cyclic ureas and related nucleophiles
Mukherjee, Paramita,Widenhoeferst, Ross A.
supporting information; experimental part, p. 1184 - 1187 (2010/05/18)
"Chemical Equation Presented" A 1:1 mixture of [P(t-Bu) 2-obiphenyl]AuCl and AgSbF6 catalyzes the intermolecular amination of allylic alcohols with 1-methylimldazolidin-2one and related nucleophiles that, In the case of γ-unsubstituted or γ-methyl- substituted allylic alcohols, occurs with high γ-regioselectivity and syn-stereoselectivlty.
Rhodium-catalyzed asymmetric hydroformylation of n-allvlamides: Highly enantioselective approach to β2-amino aldehydes
Zhang, Xiaowei,Cao, Bonan,Yu, Shichao,Zhang, Xumu
supporting information; experimental part, p. 4047 - 4050 (2010/08/07)
(Figure Presented) You're having a lahf I The asymmetric hydroformylation (AHF) of allylic compounds, catalyzed by a rhodium-yanphos complex, is a direct and concise route to ss2-amino aldehydes, acids, and alcohols with excellent enantioselectivity (see scheme; TON =turnover number, acac = acetylacetonate).
Design and synthesis of new hydroxyethylamines as inhibitors of d-alanyl-d-lactate ligase (VanA) and d-alanyl-d-alanine ligase (DdlB)
Sova, Matej,Cadez, Gasper,Turk, Samo,Majce, Vita,Polanc, Slovenko,Batson, Sarah,Lloyd, Adrian J.,Roper, David I.,Fishwick, Colin W.G.,Gobec, Stanislav
scheme or table, p. 1376 - 1379 (2009/11/30)
The Van enzymes are ATP-dependant ligases responsible for resistance to vancomycin in Staphylococcus aureus and Enteroccoccus species. The de novo molecular design programme SPROUT was used in conjunction with the X-ray crystal structure of Enterococcus faecium d-alanyl-d-lactate ligase (VanA) to design new putative inhibitors based on a hydroxyethylamine template. The two best ranked structures were selected and efficient syntheses developed. The inhibitory activities of these molecules were determined on E. faecium VanA, and due to structural similarity and a common reaction mechanism, also on d-Ala-d-Ala ligase (DdlB) from Escherichia coli. The phosphate group attached to the hydroxyl moiety of the hydroxyethylamine isostere within these systems is essential for their inhibitory activity against both VanA and DdlB.
Phosphorylated hydroxyethylamines as novel inhibitors of the bacterial cell wall biosynthesis enzymes MurC to MurF
Sova, Matej,Kovac, Andreja,Turk, Samo,Hrast, Martina,Blanot, Didier,Gobec, Stanislav
experimental part, p. 217 - 222 (2010/03/01)
Enzymes involved in the biosynthesis of bacterial peptidoglycan represent important targets for development of new antibacterial drugs. Among them, Mur ligases (MurC to MurF) catalyze the formation of the final cytoplasmic precursor UDP-N-acetylmuramyl-pentapeptide from UDP-N-acetylmuramic acid. We present the design, synthesis and biological evaluation of a series of phosphorylated hydroxyethylamines as new type of small-molecule inhibitors of Mur ligases. We show that the phosphate group attached to the hydroxyl moiety of the hydroxyethylamine core is essential for good inhibitory activity. The IC50 values of these inhibitors were in the micromolar range, which makes them a promising starting point for the development of multiple inhibitors of Mur ligases as potential antibacterial agents. In addition, 1-(4-methoxyphenylsulfonamido)-3-morpholinopropan-2-yl dihydrogen phosphate 7a was discovered as one of the best inhibitors of MurE described so far.
Synthesis of substituted 3-arylpiperidines and 3-arylpyrrolidines by radical 1,4 and 1,2-aryl migrations
Gheorghe, Alexandru,Quiclet-Sire, Béatrice,Vila, Xavier,Zard, Samir Z.
, p. 7187 - 7212 (2008/02/07)
A route to 3-arylpiperidines and 3-arylpyrrolidines involving radical 1,4- and 1,2-aryl migrations has been explored. For the piperidines, the first route requires a xanthate addition to an N-allylarylsulfonamide, followed by acetylation and treatment with lauroyl peroxide to give the corresponding 1,4-aryl transfer product. This compound can be converted into the desired piperidine derivative following acidic hydrolysis. For the second approach to piperidines, addition of an α-keto xanthate to olefins of type 14 causes 1,2-aryl migration leading to an α,β-unsaturated ester, which can be converted into a piperidine by the action of ammonia or a primary amine and sodium cyanoborohydride. Substituted 3-arylpyrrolidines can be obtained by simply starting with an α-amido substituted xanthate.
