30834-42-5Relevant articles and documents
Radical Carbonyl Umpolung Arylation via Dual Nickel Catalysis
Huang, Huan-Ming,Bellotti, Peter,Erchinger, Johannes E.,Paulisch, Tiffany O.,Glorius, Frank
supporting information, p. 1899 - 1909 (2022/02/01)
The formation of carbon-carbon bonds lies at the heart of synthetic organic chemistry and is widely applied to construct complex drugs, polymers, and materials. Despite its importance, catalytic carbonyl arylation remains comparatively underdeveloped, due
Lewis Acid Catalyzed Enantioselective Photochemical Rearrangements on the Singlet Potential Energy Surface
Leverenz, Malte,Merten, Christian,Dreuw, Andreas,Bach, Thorsten
supporting information, p. 20053 - 20057 (2019/12/30)
The oxadi-methane rearrangement of 2,4-cyclohexadienones to bicyclic ketones was found to proceed with high enantioselectivity (92-97% ee) in the presence of catalytic amounts of a chiral Lewis acid (15 examples, 52-80% yield). A notable feature of the transformation is the fact that it proceeds on the singlet hypersurface and that no triplet intermediates are involved. Rapid racemic background reactions were therefore avoided, and the catalyst loading could be kept low (10 mol %). Computational studies suggest that the enantioselectivity is determined within a Lewis acid bound singlet intermediate via a conical intersection. The utility of the method was demonstrated by a concise synthesis of the natural product trans-chrysanthemic acid.
Free-radical carbo-oximation of olefins and subsequent radical-ionic cascades
Landais, Yannick,Robert, Frédéric,Godineau, Edouard,Huet, Laurent,Likhite, Nachiket
supporting information, p. 10073 - 10080 (2013/11/06)
A sequential carbo-formylation cascade has been developed, involving a free-radical carbo-oximation process, followed by the hydrolysis of the oxime ether. For this purpose, we designed a new SEM O-protected sulfonyl oxime, which enable both rapid radical addition and hydrolysis under mild conditions. The resulting aldehyde-esters were then engaged in various nucleophilic cascades, such as Sakurai allylations or domino-Mukaiyama aldol condensation/ lactonizations. Addition of an amine and TMSCN similarly led after Strecker reaction/lactamization to α-cyano-piperidinones in good overall yield. Finally, a Pictet-Spengler/lactamization sequence was devised, which open a new entry toward the tricyclic core of eburnan alkaloids.
Molecular dynamics simulation directed rational design of inhibitors targeting drug-resistant mutants of influenza A virus M2
Wang, Jun,Ma, Chunlong,Fiorin, Giacomo,Carnevale, Vincenzo,Wang, Tuo,Hu, Fanghao,Lamb, Robert A.,Pinto, Lawrence H.,Hong, Mei,Klein, Michael L.,Degrado, William F.
supporting information; experimental part, p. 12834 - 12841 (2011/10/08)
Influenza A virus M2 (A/M2) forms a homotetrameric proton selective channel in the viral membrane. It has been the drug target of antiviral drugs such as amantadine and rimantadine. However, most of the current virulent influenza A viruses carry drug-resistant mutations alongside the drug binding site, such as S31N, V27A, and L26F, etc., each of which might be dominant in a given flu season. Among these mutations, the V27A mutation was prevalent among transmissible viruses under drug selection pressure. Until now, V27A has not been successfully targeted by small molecule inhibitors, despite years of extensive medicinal chemistry research efforts and high throughput screening. Guided by molecular dynamics (MD) simulation of drug binding and the influence of drug binding on the dynamics of A/M2 from earlier experimental studies, we designed a series of potent spirane amine inhibitors targeting not only WT, but also both A/M2-27A and L26F mutants with IC50s similar to that seen for amantadine's inhibition of the WT channel. The potencies of these inhibitors were further demonstrated in experimental binding and plaque reduction assays. These results demonstrate the power of MD simulations to probe the mechanism of drug binding as well as the ability to guide design of inhibitors of targets that had previously appeared to be undruggable.
SPIRO COMPOUNDS AND PHARMACEUTICAL USE THEREOF
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Page/Page column 35; 36, (2009/07/17)
The Spiro compound represented by the following general formula [Ia], its pharmaceutically acceptable salt or a solvate thereof
Mn(III)-Based Oxidative Fragmentation-Cyclization Reactions of Unsaturated Cyclobutanols
Snider, Barry B.,Vo, Nha Huu,Foxman, Bruce M.
, p. 7228 - 7237 (2007/10/02)
Alylic cyclobutanols 1, 10, 21, 27, 32, 39, 51 and 58 are oxidatively fragmented by Mn(OAc)3*2H2O in EtOH to give tertiary radicals as shown in eq 1.These tertiary radicals undergo both 6-endo-cyclization to the α,β-unsaturated ketone to afford α-keto rad
1,5-DICARBONYL COMPOUNDS A GENERAL PREPARATION METHOD
Duhamel, P.,Hennequin, L.,Poirier, J. M.,Tavel, G.,Vottero, C.
, p. 4777 - 4786 (2007/10/02)
In this report, a general method for the preparation of 1,5-dicarbonyl compounds and six membered ring annelation is described.This method involves the reaction of hemiacetal vinylogs 1 with enol ethers 2 or 3 in the presence of a Lewis acid.This reaction was successfully applied to the enol ethers of α and α,α'-hindered ketones such as 2,2,6-trimethyl cyclohexanone. α-Cyperone and 6-epi-α-cyperone were obtained using this process.
Geminal Acylation-Alkylation at a Carbonyl Carbon via Regiospecifically Generated Metalloenamines
Martin, Stephen F.,Phillips, Gerald W.,Puckette, Thomas A.,Colapret, John A.
, p. 5866 - 5872 (2007/10/02)
A useful procedure for effecting geminal disubstitution at the carbonyl carbon atom of aldehydes and ketones has been developed in which the sequence of reactions results in the replacement of the two carbon-oxygen bonds of the carbonyl function with an acyl group and an alkyl or hydroxyalkyl group.Of particular importance is the facile application of these procedures to the efficient construction of quaternary carbon atoms that bear alkyl appendages containing differentiated functionality.This novel methodology features the initial conversion of carbonyl compounds 1 into the substituted 2-azadienes 10 or 11 by Wittig-Horner reaction.Subsequent reaction of these 2-azadienes produced in situ with n-butyllithium results in the formation of the metalloenamines 12 and 13 (R4 = n-Bu) which undergo reactions with a wide variety of electrophiles to give, after hydrolysis of the intermediate imines, the α-substituted aldehydes 14 or the α-substituted ketones 15 in good of excellent overall yields.New procedures for the annelation of cyclopentenones such as 22 and cyclohexenones 26 at the carbonyl carbon of ketones are described as is an important variant of a directed aldol reaction, 1 --> 28.Although a number of individual manipulations are necessary to effect the geminal disubstitution of a carbonyl functional group, it is generally feasible to execute the entire sequence of reactions in single flask, thereby rendering this methodology very convenient to implement in practice.
CYCLOCARBONYLATION OF UNSATURATED TOSYLATES AS A METHOD OF CYCLANONE SYNTHESIS
McMurry, John E.,Andrus, Alex
, p. 4687 - 4690 (2007/10/02)
A study has been made to determine the scope of the cyclocarbonylation reaction of olefinic tosylates with Na2Fe(CO)4.
