Aqueous olefin metathesis: recent developments and applications

• Valerio Sabatino and
• Thomas R. Ward

Beilstein J. Org. Chem. 2019, 15, 445–468, doi:10.3762/bjoc.15.39

• water is more likely to occur at high temperatures and in the presence of a base. 1H NMR studies revealed that methanol is the source of hydride and this was later confirmed by Grubbs and co-workers [31]. The proposed mechanism for the degradation of G-I occurs via alcohol dehydrogenation followed by

Oxidative radical ring-opening/cyclization of cyclopropane derivatives

• Yu Liu,
• Qiao-Lin Wang,
• Zan Chen,
• Cong-Shan Zhou,
• Bi-Quan Xiong,
• Pan-Liang Zhang,
• Chang-An Yang and
• Quan Zhou

Beilstein J. Org. Chem. 2019, 15, 256–278, doi:10.3762/bjoc.15.23

• , phenylselenyl radical 26 was produced in the presence of free radical initiator (NH4)2S2O8 [60][61]. Next, the intermediate 26 was added to the C–C double bond of MCPs 23, and then went through a series of ring-opening, intramolecular cyclization, oxidation and dehydrogenation to generate 3

• -opening, cyclization, oxidation and dehydrogenation and successfully furnished trifluoromethylthiolated 1,2-dihydronaphthalene derivatives 39 (Scheme 10) [67]. This reaction was achieved in the presence of 3.0 equiv of Na2S2O8 as the oxidants, 0.5 equiv of HMPA (N,N,N',N',N'',N

• addition of radical 44 to the C–C double bond of MCPs 1 generats a more stable benzyl radical 45. Final ring-opening, intramolecular cyclization, oxidation, and dehydrogenation finally delivers the desired product 41. Next, our group reported the first oxidative ring-opening and cyclization between MCPs 1

First thia-Diels–Alder reactions of thiochalcones with 1,4-quinones

• Grzegorz Mlostoń,
• Katarzyna Urbaniak,
• Paweł Urbaniak,
• Anna Marko,
• Anthony Linden and
• Heinz Heimgartner

Beilstein J. Org. Chem. 2018, 14, 1834–1839, doi:10.3762/bjoc.14.156

• Department of Chemistry, University of Zurich, Winterthurerstrasse 190, CH-8057 Zurich, Switzerland 10.3762/bjoc.14.156 Abstract Aryl and hetaryl thiochalcones react smoothly with 1,4-quinones in THF solution at 60 °C yielding the corresponding fused 4H-thiopyrans after spontaneous dehydrogenation of the

One hundred years of benzotropone chemistry

• Arif Dastan,
• Haydar Kilic and
• Nurullah Saracoglu

Beilstein J. Org. Chem. 2018, 14, 1120–1180, doi:10.3762/bjoc.14.98

• ]. Firstly, dichloride 41 was reduced with LiAlH4 in ether to give the monochloride 42. The reaction of 42 with DDQ produced 4,5-benzotropone (11) in 24% yield together with 28% of starting material. The key step for 11 from 42 is the electrocyclic ring expansion of dehydrogenation product 44 to the

• carbonyl compounds and conjugated aromatic carbonyl systems. Nicolaou’s group reported a general method for the mild, swift, and highly efficient oxidation of alcohols, ketones, and aldehydes to unsaturated compounds in one pot (Scheme 30) [138][139]. Accordingly, an IBX-controlled dehydrogenation through

• selenium dioxide in boiling ethanol, followed by dehydrogenation with bromine in acetic acid at 100 °C. Another method for the synthesis of 7-hydroxy-2,3-benzotropone (241) starting from the reaction of diketone 276 with boiling acetic anhydride was achieved by Maignan (Scheme 44) [168]. The reaction of

Progress in copper-catalyzed trifluoromethylation

• Guan-bao Li,
• Chao Zhang,
• Chun Song and
• Yu-dao Ma

Beilstein J. Org. Chem. 2018, 14, 155–181, doi:10.3762/bjoc.14.11

• presence of copper reagent. Then, the trifluoromethyl radical reacts with substrates affording intermediate A, which may be oxidized to a carbocation B, followed by an oxidative dehydrogenation process delivering the target product. Copper-mediated/catalyzed direct trifluoromethylation of C(sp)–H

Aminomethylation/hydrogenolysis as an alternative to direct methylation of metalated isoquinolines – a novel total synthesis of the alkaloid 7-hydroxy-6-methoxy-1-methylisoquinoline

• Benedikt C. Melzer,
• Jan G. Felber and
• Franz Bracher

Beilstein J. Org. Chem. 2018, 14, 130–134, doi:10.3762/bjoc.14.8

• been reported so far. Further, this literature search showed that two total syntheses of isoquinoline 1 had been published even before its identification as a natural product (Figure 1). In 1963, Franck and Blaschke [11] obtained 1 by dehydrogenation of its 1,2,3,4-tetrahydro analogue (which itself had

Quinone-catalyzed oxidative deformylation: synthesis of imines from amino alcohols

• Xinyun Liu,
• Johnny H. Phan,
• Benjamin J. Haugeberg,
• Shrikant S. Londhe and
• Michael D. Clift

Beilstein J. Org. Chem. 2017, 13, 2895–2901, doi:10.3762/bjoc.13.282

• preparation of imines (Scheme 1). The condensation of an amine with an aldehyde or ketone is the oldest and most commonly employed method for imine synthesis [4]. More recently, the catalytic dehydrogenation of amines mediated by metal and organic catalysts has begun to emerge as an alternative approach for

Vinylphosphonium and 2-aminovinylphosphonium salts – preparation and applications in organic synthesis

• Anna Kuźnik,
• Roman Mazurkiewicz and
• Beata Fryczkowska

Beilstein J. Org. Chem. 2017, 13, 2710–2738, doi:10.3762/bjoc.13.269

• expected ylide 97. The subsequent intramolecular Wittig reaction in boiling toluene gave the 1,2-dihydroquinoline derivatives 98, which underwent dehydrogenation into the corresponding 4-arylquinolines 99 in yields of 55–90% (Scheme 57) [70]. In an analogous manner, Yavari and Mosslemin synthesized furan

NHC-catalyzed cleavage of vicinal diketones and triketones followed by insertion of enones and ynones

• Ken Takaki,
• Makoto Hino,
• Akira Ohno,
• Kimihiro Komeyama,
• Hiroto Yoshida and
• Hiroshi Fukuoka

Beilstein J. Org. Chem. 2017, 13, 1816–1822, doi:10.3762/bjoc.13.176

• recently obtained by the dimsyl anion-promoted double acylation of enones with benzils, followed by dehydrogenation of the resulting alkanes in one pot [16]. Moreover, if the reaction of cyclic 1,2-diketone I (G = C(O)R1) with activated alkenes may take place similarly, this reaction could be utilized as a

Oxidative dehydrogenation of C–C and C–N bonds: A convenient approach to access diverse (dihydro)heteroaromatic compounds

• Santanu Hati,
• Ulrike Holzgrabe and
• Subhabrata Sen

Beilstein J. Org. Chem. 2017, 13, 1670–1692, doi:10.3762/bjoc.13.162

• /bjoc.13.162 Abstract Nitrogen heteroarenes form an important class of compounds which can be found in natural products, synthetic drugs, building blocks etc. Among the diverse strategies that were developed for the synthesis of nitrogen heterocycles, oxidative dehydrogenation is extremely effective

• . This review discusses various oxidative dehydrogenation strategies of C–C and C–N bonds to generate nitrogen heteroarenes from their corresponding heterocyclic substrates. The strategies are categorized under stoichiometric and catalytic usage of reagents that facilitate such transformations. The

• application of these strategies in the synthesis of nitrogen heteroarene natural products and synthetic drug intermediates are also discussed. We hope this review will arouse sufficient interest among the scientific community to further advance the application of oxidative dehydrogenation in the synthesis of

Cycloheximide congeners produced by Streptomyces sp. SC0581 and photoinduced interconversion between (E)- and (Z)-2,3-dehydroanhydrocycloheximides

• Li Yang,
• Ping Wu,
• Jinghua Xue,
• Huitong Tan,
• Zheng Zhang and
• Xiaoyi Wei

Beilstein J. Org. Chem. 2017, 13, 1039–1049, doi:10.3762/bjoc.13.103

• 2 and 3 was observed and verified and the possible reaction path and mechanism were proposed by theoretical computations. The antifungal and cytotoxic activities of 1–6 were evaluated and suggested that 2,3-dehydrogenation results in the loss of the activities and supported that the OH-α is

• of cycloheximide derivatives (4 vs 6) [21][22], and suggested that 2,3-dehydrogenation might result in the loss of the activity (1 vs 5, 6). The cytotoxicity of these isolates against human lung epithelial carcinoma (A549), human cervical epithelial adenocarcinoma (HeLa), and human breast carcinoma

Isoxazole derivatives as new nitric oxide elicitors in plants

• Anca Oancea,
• Emilian Georgescu,
• Florentina Georgescu,
• Alina Nicolescu,
• Elena Iulia Oprita,
• Catalina Tudora,
• Lucian Vladulescu,
• Marius-Constantin Vladulescu,
• Florin Oancea and
• Calin Deleanu

Beilstein J. Org. Chem. 2017, 13, 659–664, doi:10.3762/bjoc.13.65

• situ by the oxidative dehydrogenation of aldoximes in the presence of various oxidants [26][27][28][29], or by the dehydrohalogenation of hydroxyiminoyl halides promoted by organic or inorganic bases [30][31][32]. A less used synthetic procedure involves the oxidative dehydration of primary nitro

Synthesis of 1-indanones with a broad range of biological activity

• Marika Turek,
• Dorota Szczęsna,
• Marek Koprowski and
• Piotr Bałczewski

Beilstein J. Org. Chem. 2017, 13, 451–494, doi:10.3762/bjoc.13.48

• derivative 265 having the steroid framework from 1,2-dihydro-7-methoxy-4-vinylnaphthalene (262) and α-bromo substituted cyclopentenone 263 by the SnCl4-catalyzed Diels–Alder cycloaddition [102]. In this reaction, 1-indanone 265 was obtained in 59% yield via dehydrogenation of a mixture of cycloadducts 264a–c

A new paradigm for designing ring construction strategies for green organic synthesis: implications for the discovery of multicomponent reactions to build molecules containing a single ring

• John Andraos

Beilstein J. Org. Chem. 2016, 12, 2420–2442, doi:10.3762/bjoc.12.236

• containing one asymmetric feature, namely the electrophilic carbonyl group. This molecule is made industrially from precursors that already have the 6-membered ring preformed [132]. Example routes include dehydrogenation of cyclohexanol, which in turn is made either by catalytic hydrogenation of phenol

Biosynthesis of oxygen and nitrogen-containing heterocycles in polyketides

• Franziska Hemmerling and
• Frank Hahn

Beilstein J. Org. Chem. 2016, 12, 1512–1550, doi:10.3762/bjoc.12.148

• the respective olefins are much lower than the analogous epoxides 53–61 suggests that epoxidation has a strong influence on the performance of the downstream enzymes. The dioxygenase MupW together with its associated ferredoxin dioxygenase MupT then catalyse dehydrogenation and epoxidation on C8 and

Stereoselective synthesis of tricyclic compounds by intramolecular palladium-catalyzed addition of aryl iodides to carbonyl groups

• Jakub Saadi,
• Christoph Bentz,
• Kai Redies,
• Dieter Lentz,
• Reinhold Zimmer and
• Hans-Ulrich Reissig

Beilstein J. Org. Chem. 2016, 12, 1236–1242, doi:10.3762/bjoc.12.118

• this study [30]. Possible mechanisms for this process leading to the formation of an iminium intermediate or a dehydrogenation of the amine are depicted in Scheme 10. Conclusion We have found new examples of intramolecular palladium-catalyzed nucleophilic additions of aryl iodides to alkyl ketones

Indenopyrans – synthesis and photoluminescence properties

• Andreea Petronela Diac,
• Ana-Maria Ţepeş,
• Albert Soran,
• Ion Grosu,
• Anamaria Terec,
• Jean Roncali and
• Elena Bogdan

Beilstein J. Org. Chem. 2016, 12, 825–834, doi:10.3762/bjoc.12.81

• obtain photoluminescent compounds with higher performance, the dehydrogenation reaction of enol-lactones 2 and 3 was performed. Adapted from a procedure previously described [38], the oxidation of the isomeric mixture 2'a/3''a and 2'c/3'c, respectively, in the presence of 2,3-dichloro-5,6-dicyano-1,4

• -benzoquinone (DDQ), led to indeno-α-pyrones 4–6 (Scheme 2), in not very satisfying yields. Investigations carried out for the dehydrogenation reaction of the isomeric mixture 2'a/3''a (Scheme 2) revealed the formation of the α-pyrone 6a (15% yield), which was the oxidation product of isomer 3''a. In the same

• time, most of the isomer 2'a was recovered and traces of derivative 4a could only be detected in the NMR spectrum. Using the same procedure, the enol-lactone isomeric mixture 2'c/3'c was subjected to the dehydrogenation reaction yielding the regioisomers 4c and 5c (Scheme 2). The 1H NMR spectrum

Opportunities and challenges for direct C–H functionalization of piperazines

• Zhishi Ye,
• Kristen E. Gettys and
• Mingji Dai

Beilstein J. Org. Chem. 2016, 12, 702–715, doi:10.3762/bjoc.12.70

• tetrahydroisoquinoline [53][54] gave the carbonylation product directly. However, when piperazine substrates were used, an additional formal dehydrogenation process took place before the carbonylation reaction. As shown in Figure 13, under the conditions of 15 atm of carbon monoxide and ethylene, Rh4(CO)12 catalyst, and

• toluene at 160 °C, dehydrogenation and propionylation of N-(2-pyridinyl)piperazines took place to give various tetrahydropiperazines. Similar to the α-C–H lithiation trapping strategy, the substituents on the distal nitrogen have a profound effect on the overall yield with alkyl groups giving better

• dehydrogenation products were observed. Overall, the result is promising, but this method has quite a limited substrate scope and yields only dehydrogenated products after C–H functionalization instead of the desired fully saturated piperazines. It also highlights the challenges provided by the extra nitrogen of

Cascade alkylarylation of substituted N-allylbenzamides for the construction of dihydroisoquinolin-1(2H)-ones and isoquinoline-1,3(2H,4H)-diones

• Ping Qian,
• Bingnan Du,
• Wei Jiao,
• Haibo Mei,
• Jianlin Han and
• Yi Pan

Beilstein J. Org. Chem. 2016, 12, 301–308, doi:10.3762/bjoc.12.32

• [18][19], decarboxylative alkenylation of cycloalkanes with aryl vinylic carboxylic acids [20][21], trifluoromethylthiolation [22], thiolation [23][24], alkenylation [25][26], dehydrogenation−olefination and esterification [27][28], radical addition/1,2-aryl migration [29], cascade alkylation

Biocatalysis for the application of CO₂ as a chemical feedstock

• Apostolos Alissandratos and
• Christopher J. Easton

Beilstein J. Org. Chem. 2015, 11, 2370–2387, doi:10.3762/bjoc.11.259

Stereoselective synthesis of hernandulcin, peroxylippidulcine A, lippidulcines A, B and C and taste evaluation

• Marco G. Rigamonti and
• Francesco G. Gatti

Beilstein J. Org. Chem. 2015, 11, 2117–2124, doi:10.3762/bjoc.11.228

• reagent. The taste evaluations indicate that none of these sesquiterpenes are sweet, instead the lippidulcine A is a cooling agent with a mint after taste. Keywords: ADH ketone reduction; cooling agent; Corey–Bakshi–Shibata reduction; dehydrogenation; hernandulcin; Kornblum–DeLaMare rearrangement

• to −30 °C). Treatment of 7 with Dess–Martin periodinane (DMP) [23] in CH2Cl2 at room temperature gave ketone 8 ([α]D +11.0° (c 1.0, CHCl3)) in 90% yield. The most difficult step of this synthetic route is the dehydrogenation of ketone 8. Since our main interest is focused on the taste evaluation of

• Pd(TFA)2 catalyzed dehydrogenation on the silyl enol ether 10 and in the presence of Na2HPO4 buffer, in order to mitigate the detrimental acidity of TFA. However, 11 was produced in a modest yield of 21%, because, even at these mild conditions, 10 reconverted to the initial ketone 9 faster than its

Selected synthetic strategies to cyclophanes

• Sambasivarao Kotha,
• Mukesh E. Shirbhate and
• Gopalkrushna T. Waghule

Beilstein J. Org. Chem. 2015, 11, 1274–1331, doi:10.3762/bjoc.11.142

Glycoluril–tetrathiafulvalene molecular clips: on the influence of electronic and spatial properties for binding neutral accepting guests

• Yoann Cotelle,
• Marie Hardouin-Lerouge,
• Stéphanie Legoupy,
• Olivier Alévêque,
• Eric Levillain and
• Piétrick Hudhomme

Beilstein J. Org. Chem. 2015, 11, 1023–1036, doi:10.3762/bjoc.11.115

• onto compound 11 [34]. The hydroquinone moieties were subjected to a dehydrogenation reaction using DDQ in THF to reach desired glycolurildiquinone 13 [35] in 91% yield. The Diels–Alder cycloaddition was carried out by treatment of bis-dienophile 13 with TTF derivative 14 [36], able to give rise in

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

• radical mechanisms were proposed, the common feature is the generation of alkene via the radical dehydrogenation of alkane. 2.6 Other oxidative systems Esters were synthesized from aldehydes and methanol (6 equiv excess relative to aldehyde) using pyridinium dichromate in DMF [170]. Methyl esters were

• afforded molecular hydrogen and unsymmetrical ester 187 (Scheme 39) [182]. Cross-coupling products 187 were obtained in high yields; the expected homocoupling of primary alcohols giving symmetrical esters and the dehydrogenation of secondary alcohols yielding ketones were avoided. 3 Ketones and 1,3

Electrocarboxylation: towards sustainable and efficient synthesis of valuable carboxylic acids

• Roman Matthessen,
• Jan Fransaer,
• Koen Binnemans and
• Dirk E. De Vos

Beilstein J. Org. Chem. 2014, 10, 2484–2500, doi:10.3762/bjoc.10.260

• for the polymer industry. 1,3-Butadiene is widely available, not only from steam cracking, but increasingly from dehydrogenation of linear butenes. Dicarboxylation of 1,3-butadiene yields a mixture of 3-hexene-1,6-dioic acid isomers, which are only one hydrogenation step removed from adipic acid, a