Rearrangements of organic peroxides and related processes

• Ivan A. Yaremenko,
• Vera A. Vil’,
• Dmitry V. Demchuk and
• Alexander O. Terent’ev

Beilstein J. Org. Chem. 2016, 12, 1647–1748, doi:10.3762/bjoc.12.162

• the synthesis of functionalized ketones and alcohols, including γ-hydroxy enones. The Dakin oxidation finds application for the synthesis of phenols from arylaldehydes or aryl ketones and the Elbs persulfate oxidation allows the preparation of hydroxyphenols from phenols. Finally, the Schenck and

Synthesis of 2-substituted tetraphenylenes via transition-metal-catalyzed derivatization of tetraphenylene

• Shulei Pan,
• Hang Jiang,
• Yanghui Zhang,
• Yu Zhang and
• Dushen Chen

Beilstein J. Org. Chem. 2016, 12, 1302–1308, doi:10.3762/bjoc.12.122

• into other functionalities [58][59]. The Larock group reported a novel Pd-catalyzed addition of nitriles to an arene C–H bond for the synthesis of aryl ketones [60][61]. Following the Larock’s conditions, we investigated the carbonylation of tetraphenylene (1) and the carbonylated product 5a was

Conjugate addition–enantioselective protonation reactions

• James P. Phelan and
• Jonathan A. Ellman

Beilstein J. Org. Chem. 2016, 12, 1203–1228, doi:10.3762/bjoc.12.116

• . Solvent mixtures of water and THF or ethanol also provided poor reactivity and enantioselectivity. A variety of electron-rich and electron-poor aryl ketones and benzylic thiols were effective substrates. The authors observed that a fast racemic background reaction proceeded in the presence of pyridine

Biradical vs singlet oxygen photogeneration in suprofen–cholesterol systems

• Fabrizio Palumbo,
• Francisco Bosca,
• Isabel M. Morera,
• Inmaculada Andreu and
• Miguel A. Miranda

Beilstein J. Org. Chem. 2016, 12, 1196–1202, doi:10.3762/bjoc.12.115

• singlet oxygen, thus being able to initiate Ch oxidation from their triplet excited states following either of the two competing mechanistic pathways. Keywords: aryl ketones; hydrogen abstraction; lipid peroxidation; photoproducts; triplet excited state; Introduction Among the constituents of cell

Hydrogenation of unactivated enamines to tertiary amines: rhodium complexes of fluorinated phosphines give marked improvements in catalytic activity

• Sergey Tin,
• Tamara Fanjul and
• Matthew L. Clarke

Beilstein J. Org. Chem. 2015, 11, 622–627, doi:10.3762/bjoc.11.70

• triacetoxyborohydride or sodium cyanoborohydride can be appealing at small scale where the practical issues noted above are not so important. However, the formation of tertiary amines from aryl ketones using hydride reagents has been reported to be problematic [31]. In addition, the hydride reductions, whether carried

Cross-dehydrogenative coupling for the intermolecular C–O bond formation

• Igor B. Krylov,
• Vera A. Vil’ and
• Alexander O. Terent’ev

Beilstein J. Org. Chem. 2015, 11, 92–146, doi:10.3762/bjoc.11.13

• observed due, apparently, to the addition of the C-radical generated from ketone to benzene [204]. It was shown [209] that the α’-acetoxylation of enones occurs with good selectivity in other solvents, such as cyclohexane and acetonitrile, as well. The acyloxylation of enones and aryl ketones 220 with

(CF₃CO)₂O/CF₃SO₃H-mediated synthesis of 1,3-diketones from carboxylic acids and aromatic ketones

• JungKeun Kim,
• Elvira Shokova,
• Victor Tafeenko and
• Vladimir Kovalev

Beilstein J. Org. Chem. 2014, 10, 2270–2278, doi:10.3762/bjoc.10.236

• in the phenyl moiety. On the basis of the above results, we supposed that the acylation of ketones with carboxylic acids in a TFAA/TfOH/CH2Cl2 system could be applied as an effective method for the synthesis of β-diketone. It turned out that the acylation of different alkyl aryl ketones 2a–k

Photorelease of phosphates: Mild methods for protecting phosphate derivatives

• Sanjeewa N. Senadheera,
• Abraham L. Yousef and
• Richard S. Givens

Beilstein J. Org. Chem. 2014, 10, 2038–2054, doi:10.3762/bjoc.10.212

• modest efficiency, Φ = 0.028. Similarly, the methoxy analog, 1,4-MNA DEP (14b), released DEP, but with a much lower efficiency (Φ = 0.0078). Both quantitatively produced DEP and, pleasingly, underwent photo-Favorskii rearrangements converting the aryl ketones to methyl naphthylacetates, blue-shifting the

Additive-assisted regioselective 1,3-dipolar cycloaddition of azomethine ylides with benzylideneacetone

• Chuqin Peng,
• Jiwei Ren,
• Jun-An Xiao,
• Honggang Zhang,
• Hua Yang and
• Yiming Luo

Beilstein J. Org. Chem. 2014, 10, 352–360, doi:10.3762/bjoc.10.33

• with various dipolarophiles, such as α,β-unsaturated esters [21][22][23][24][25], dienones [26][27], α,β-unsaturated ketones [28][29][30], unsaturated aryl ketones [31][32][33] and electron-poor alkenes [34][35][36][37][38][39]. Among the studied α,β-unsaturated enones for 1,3-dipolar cycloaddition

Carbenoid-mediated nucleophilic “hydrolysis” of 2-(dichloromethylidene)-1,1,3,3-tetramethylindane with DMSO participation, affording access to one-sidedly overcrowded ketone and bromoalkene descendants^§

• Rudolf Knorr,
• Thomas Menke,
• Johannes Freudenreich and
• Claudio Pires

Beilstein J. Org. Chem. 2014, 10, 307–315, doi:10.3762/bjoc.10.28

• mechanistic considerations for the unusual “hydrolysis” reaction of the unactivated α,α-dichloroalkene 6 and its side-products. Toward one-sidedly overcrowded ketone and bromoalkene descendants The α,α-(di-tert-alkyl)methyl aryl ketones 38 (Scheme 6) would normally be considered to be accessible through

CuCl-catalyzed aerobic oxidation of 2,3-allenols to 1,2-allenic ketones with 1:1 combination of phenanthroline and bipyridine as ligands

• Shuxu Gao,
• Yu Liu and
• Shengming Ma

Beilstein J. Org. Chem. 2011, 7, 396–403, doi:10.3762/bjoc.7.51

• CuCl, 10 mol % of 1,10-phenanthroline, 10 mol % of 2,2'-bipyridine and 50 mol % of K2CO3 in toluene with air (300 psi, 35 °C) as the oxidant were defined as the standard conditions. Under the standard conditions a series of 1-aryl-2,3-allenols were oxidized to the corresponding 1,2-allenic aryl ketones

Chemoselective reduction of aldehydes by ruthenium trichloride and resin- bound formates

• Basudeb Basu,
• Bablee Mandal,
• Sajal Das,
• Pralay Das and
• Ashis K. Nanda

Beilstein J. Org. Chem. 2008, 4, No. 53, doi:10.3762/bjoc.4.53

• -donor, in the presence of catalytic ruthenium trichloride is described. Aromatic aldehydes and 1,2-diketones are reduced efficiently and selectively, while aryl ketones remain unchanged. Several other potentially reducible groups attached to the aromatic moiety are unaffected. Keywords: Amberlite

• [25]. Pd-catalyzed transfer hydrogenation of nitroarenes using recyclable polymer-supported formate has been investigated by Abiraj et al [26]. Neither of these conditions were, however, effective in reducing aryl ketones. Since aryl alcohols are important compounds, we became interested to look at

• the ability of Ru(III) salts in the CTH of aryl ketones using the poly-ionic resin formate. Our studies reported herein constitute an efficient method for chemoselective transfer hydrogenation of aryl aldehydes with the aid of resin-supported formate in the presence of catalytic (2.5 mol%) amount of

Hydrogenation of aromatic ketones, aldehydes, and epoxides with hydrogen and Pd(0)EnCat™ 30NP

• Steven V. Ley,
• Angus J. P. Stewart-Liddon,
• David Pears,
• Remedios H. Perni and
• Kevin Treacher

Beilstein J. Org. Chem. 2006, 2, No. 15, doi:10.1186/1860-5397-2-15

• University described the selective reduction of electron deficient and neutral aryl ketones to benzylic alcohols using Pd(0)EnCat™ 30NP as catalyst and a mixture of HCOOH/Et3N as the source of hydrogen [16]. Under these conditions they also achieved the chemoselective hydrogenolysis of aryl epoxides [17

• or Pd/Al2O3. Pd(0)EnCat™ 30NP-catalyzed hydrogenation of 4-mathoxybenzaldehyde and 4-methoxyacetophenone. Comparison with other Pd catalysts. Pd(0)EnCat™30NP-catalyzed hydrogenation of aryl ketones and aldehydes. Pd(0)EnCat™ 30NP-Catalyzed Hydrogenolysis of trans-stilbene oxide. Comparison with other

• recycling of the catalyst problematic. Addition of NaOH or designing bimetallic catalysts in which one of the metals acts as poisoning agent, have also been reported. [8][9][10] Several metals (e.g. Pd, Pt, Ru) have been used in the literature for the selective heterogeneous catalytic reduction of aryl