Recent applications of the divinylcyclopropane–cycloheptadiene rearrangement in organic synthesis

• Sebastian Krüger and
• Tanja Gaich

Beilstein J. Org. Chem. 2014, 10, 163–193, doi:10.3762/bjoc.10.14

• -exo-dig fashion. Radical quenching gave cis-arylvinylcyclopropane 238. Arylvinylcyclopropane rearrangement was followed by rearomatization to give tetracycle 239 (see Scheme 29). Padwa and coworkers [201] discovered an intermediate DVCPR during their investigation of rhodium-catalyzed cyclizations of

Synthesis of five- and six-membered cyclic organic peroxides: Key transformations into peroxide ring-retaining products

• Alexander O. Terent'ev,
• Dmitry A. Borisov,
• Vera A. Vil’ and
• Valery M. Dembitsky

Beilstein J. Org. Chem. 2014, 10, 34–114, doi:10.3762/bjoc.10.6

• synthesized in a similar way starting with the peroxidation of 2-methyl-2-(3-methylbut-3-enyl)oxetane (222), followed by oxetane-ring opening in triethyl(2-methyl-4-(2-methyloxetan-2-yl)butan-2-ylperoxy)silane (223) (Scheme 63) [250]. Dioxanes can also be synthesized by inramolecular cyclizations with the

• acetate-catalyzed synthesis of cyclic peroxides [336]. 3.10. Acid-mediated cyclizations of peroxides The intramolecular cyclization of unsaturated peroxyacetals 273a–d in the presence of TiCl4 or SnCl4 occurs via formation of peroxycarbenium ions to give methoxy- and chlorine-containing dioxanes 274a–d as

The renaissance of organic radical chemistry – deja vu all over again

• Corey R. J. Stephenson,
• Armido Studer and
• Dennis P. Curran

Beilstein J. Org. Chem. 2013, 9, 2778–2780, doi:10.3762/bjoc.9.312

• of organic radical chemistry that delivered groundbreaking results, especially in organic synthesis. By the 1990’s, radical reactions (especially cyclizations) were broadly recognized as powerful tools to make molecules. This Renaissance I in organic radical chemistry was built on prior renaissances

Garner’s aldehyde as a versatile intermediate in the synthesis of enantiopure natural products

• Mikko Passiniemi and
• Ari M.P. Koskinen

Beilstein J. Org. Chem. 2013, 9, 2641–2659, doi:10.3762/bjoc.9.300

• with Red-Al. Both isomers B and C can also be directly accessed from 1 with the corresponding cis- and trans-vinyl nucleophiles. Allylic alcohol B can be used as an intermediate in the synthesis of various natural products or intermediates thereof. The cis-double bond allows cyclizations to five- or

Gold(I)-catalyzed domino cyclization for the synthesis of polyaromatic heterocycles

• Mathieu Morin,
• Patrick Levesque and
• Louis Barriault

Beilstein J. Org. Chem. 2013, 9, 2625–2628, doi:10.3762/bjoc.9.297

• cyclizations of the enol ether 11a (R1 = p-BrC6H4, R2 = H) gave the corresponding benzothiophene 12a in 83% yield. The use of electron-poor silyl enol ether 11b (R1 = p-NO2C6H4, R2 = H) gave the desired product 12b, albeit in lower yield of 63%. Di- and trisubstituted silyl enol ethers 11c (R1 and R2 = H) and

Gold(I)-catalyzed enantioselective cycloaddition reactions

• Fernando López and
• José L. Mascareñas

Beilstein J. Org. Chem. 2013, 9, 2250–2264, doi:10.3762/bjoc.9.264

• , aldol reactions, 1,3-dipolar cycloadditions, and cyclizations [13][14][15]. Other gold-promoted asymmetric induction strategies rely on the use of chiral counterions. Indeed, it has been shown that a tight chiral ion pair with the gold cation is able to induce excellent levels of asymmetry in certain

• cyclizations [16]. Cycloaddition reactions are very important synthetic processes that allow the transformation of simple acyclic precursors into complex cyclic or polycyclic adducts in a rapid and efficient way [17][18], usually providing a rapid increase in skeletal and stereochemical complexity. Moreover

Gold(I)-catalyzed formation of furans from γ-acyloxyalkynyl ketones

• Marie Hoffmann,
• Solène Miaskiewicz,
• Jean-Marc Weibel,
• Patrick Pale and
• Aurélien Blanc

Beilstein J. Org. Chem. 2013, 9, 1774–1780, doi:10.3762/bjoc.9.206

• construct the furan motif [4][5]. Among them, late transition metal-catalyzed intra- or intermolecular cyclizations of oxygenated functionalities on unsaturated carbon–carbon bonds proved to be powerful synthetic methods due to their mildness, efficiency and diversity [6][7]. In the last decade, gold

Gold-catalyzed cyclization of allenyl acetal derivatives

• Dhananjayan Vasu,
• Samir Kundlik Pawar and
• Rai-Shung Liu

Beilstein J. Org. Chem. 2013, 9, 1751–1756, doi:10.3762/bjoc.9.202

• intermediates I encourages us to understand their behavior in the absence of a dipolarophile. This work reports gold-catalyzed intramolecular cyclizations of these allenyl acetals [19]. Results and Discussion We first tested the intramolecular cyclizations of allenyl acetal 1a with PPh3AuCl/AgSbF6 (5 mol

• highlights the diversified mechanism of such oxidative cyclizations. We prepared the additional substrates 5b–5g bearing an acetate group to examine the scope of the reaction, results are shown in Table 3. This gold-catalyzed cyclization was applicable to compound 5b bearing a cyclopentyl bridge, giving the

Anodic coupling of carboxylic acids to electron-rich double bonds: A surprising non-Kolbe pathway to lactones

• Robert J. Perkins,
• Hai-Chao Xu,
• John M. Campbell and
• Kevin D. Moeller

Beilstein J. Org. Chem. 2013, 9, 1630–1636, doi:10.3762/bjoc.9.186

• form product 9. No product from sulfonamide trapping (8) was observed. However, when the reaction was run under more basic conditions (0.5 equivalents of lithium methoxide) cyclic voltammetry data indicated that the oxidative cyclizations were initiated by the oxidation of sulfonamide anion. This led

• to initial formation of N-localized radical 6. Depending on the reaction conditions, the experiment favoured either a sulfonamide or alcohol based cyclization. Density functional theory (DFT) calculations suggested that sulfonamide based cyclizations proceed by addition of the N-localized radical to

• the ketene dithioacetal in the absence of a trapping group [21]. The anodic coupling of a carboxylic acid group with a vinyl sulfide and an enol ether were also examined (Table 2). As with earlier alcohol and amine based cyclizations, reactions with the vinyl sulfide coupling partner proceeded much

Computational study of the rate constants and free energies of intramolecular radical addition to substituted anilines

• Andreas Gansäuer,
• Meriam Seddiqzai,
• Tobias Dahmen,
• Rebecca Sure and
• Stefan Grimme

Beilstein J. Org. Chem. 2013, 9, 1620–1629, doi:10.3762/bjoc.9.185

• the addition is about as fast as the 6-endo cyclization of the hexenyl radical. Such reactions and other even slower cyclizations are well documented in titanocene mediated and catalyzed radical processes [61][62][63][64][65][66][67][68][69]. Therefore, the relatively high computational rate constant

Mechanistic studies on the CAN-mediated intramolecular cyclization of δ-aryl-β-dicarbonyl compounds

• Brian M. Casey,
• Dhandapani V. Sadasivam and
• Robert A. Flowers II

Beilstein J. Org. Chem. 2013, 9, 1472–1479, doi:10.3762/bjoc.9.167

• functionalized aromatic substrates undergo intramolecular cyclizations generating 2-tetralone derivatives in moderate to good yields. DFT computational studies indicate that successful formation of 2-tetralones from δ-aryl-β-dicarbonyl radicals is dependent on the stability of the subsequent cyclohexadienyl

• group was at the meta position (Table 2, entry 4). For substrates 1e and 1f with the methoxy group at either the ortho or para position, respectively, methyl esters 2e and 2f (Table 2, entries 2 and 3) were the major products. Additionally, intramolecular cyclizations with electron-deficient δ-aryl

• explain the site-selective radical cyclizations with m-methoxylated rings, the selectivity of naphthyl substrates was not investigated. The energy values for the cyclization of all substituents are given in Table 3, and their corresponding energy diagrams are given in Figure 1. For unsubstituted 1a’, the

Exploration of an epoxidation–ring-opening strategy for the synthesis of lyconadin A and discovery of an unexpected Payne rearrangement

• Brad M. Loertscher,
• Yu Zhang and
• Steven L. Castle

Beilstein J. Org. Chem. 2013, 9, 1179–1184, doi:10.3762/bjoc.9.132

• efficiently furnish its bicyclo[5.4.0]undecane system, which is shown in bold in Figure 1. Subsequent to this observation, we performed model studies that demonstrated the viability of highly stereoselective 7-exo-trig acyl radical–6-exo-trig alkyl radical cyclizations as a means of preparing bicyclo[5.4.0

Cascade radical reaction of substrates with a carbon–carbon triple bond as a radical acceptor

• Hideto Miyabe,
• Ryuta Asada and
• Yoshiji Takemoto

Beilstein J. Org. Chem. 2013, 9, 1148–1155, doi:10.3762/bjoc.9.128

• (Figure 1) [37][38][39][40][41][42][43]. Enantioselective radical reactions have been intensively studied over the past fifteen years. Compared with stereocontrol studies on intermolecular radical reactions, the enantioselective stereocontrol in radical cyclizations still remains a major challenge [44][45

• addition–cyclization–trapping reaction of substrates with a carbon–carbon triple bond as a radical acceptor as well as the scope and limitation of hydroxamate ester as a coordination site with a chiral Lewis acid. Synthetic strategies involving enantioselective radical cyclizations would be desirable tools

Tandem dinucleophilic cyclization of cyclohexane-1,3-diones with pyridinium salts

• Mostafa Kiamehr,
• Firouz Matloubi Moghaddam,
• Satenik Mkrtchyan,
• Volodymyr Semeniuchenko,
• Linda Supe,
• Alexander Villinger,
• Peter Langer and
• Viktor O. Iaroshenko

Beilstein J. Org. Chem. 2013, 9, 1119–1126, doi:10.3762/bjoc.9.124

• access to a number of bicyclic systems. Some of these reactions, such as the cyclization with quinazolinium salts, proceeded as one-pot cyclizations. Other cyclizations, such as the reaction with isoquinolinium salts, had to be carried out in two steps (formation of open-chained condensation products

• . Further studies to extend the scope of the synthetic utility of these cyclizations are in progress in both of our laboratories. Experimental General Information Solvents were purchased from ACROS and directly used without further purification. Analytical thin-layer chromatography was performed on 0.20 mm

Gold-catalyzed oxycyclization of allenic carbamates: expeditious synthesis of 1,3-oxazin-2-ones

• Benito Alcaide,
• Pedro Almendros,
• M. Teresa Quirós and
• Israel Fernández

Beilstein J. Org. Chem. 2013, 9, 818–826, doi:10.3762/bjoc.9.93

• ][37][38][39][40][41]. The Boc protective group has been widely used in allene chemistry, being an inert and recommended partner in gold- and palladium-catalyzed aminocyclizations of allenes [42]. On the other hand, reports of gold-catalyzed cyclizations leading to heterocycles that contain more than

Intramolecular carbolithiation cascades as a route to a highly strained carbocyclic framework: competition between 5-exo-trig ring closure and proton transfer

• William F. Bailey and
• Justin D. Fair

Beilstein J. Org. Chem. 2013, 9, 537–543, doi:10.3762/bjoc.9.59

• intramolecular 5-exo-trig ring closure has been well documented, and the absence of proton transfers that would compromise such cyclizations is a hallmark of this chemistry. In an effort to explore the limitations of this approach to more highly strained systems, the preparation of a stellane (tricyclo

• [3.3.0.03,7]octane) framework by an intramolecular carbolithiation cascade involving three coupled 5-exo-trig cyclizations of the vinyllithium derived from 2-bromo-4-vinyl-1,6-heptadiene by lithium–bromine exchange was investigated. The cascade does not afford the stellane; rather, the cascade is terminated

• after two cyclizations by a proton transfer that occurs by an intermolecular process catalyzed by trace amounts of endo-5-methyl-2-methylenebicyclo[2.2.1]heptane present in reaction mixtures as a consequence of inadvertent quenching of an intermediate alkyllithium during prolonged reaction times at room

Microwave-assisted three-component domino reaction: Synthesis of indolodiazepinotriazoles

• Rajesh K. Arigela,
• Sudhir K. Sharma,
• Brijesh Kumar and
• Bijoy Kundu

Beilstein J. Org. Chem. 2013, 9, 401–405, doi:10.3762/bjoc.9.41

• 1,3-dipolar cycloaddition reactions have been also applied by us and others with the view to synthesize triazole-annulated polyheterocycles. Although these cyclizations have been successfully carried out in either one-pot [22][23][24] or multistep format [25][26][27][28], reports involving their

Inter- and intramolecular enantioselective carbolithiation reactions

• Asier Gómez-SanJuan,
• Nuria Sotomayor and
• Esther Lete

Beilstein J. Org. Chem. 2013, 9, 313–322, doi:10.3762/bjoc.9.36

• , the aryllithium intermediate undergoes a tandem carbolithiation–γ-elimination leading to enantioenriched 2-cyclopropylphenols [51]. As shown, these enantioselective intramolecular cyclizations are mostly employed for the formation of five-membered rings. The 6-exo cyclization of an aryllithium

Polar reactions of acyclic conjugated bisallenes

• Reiner Stamm and
• Henning Hopf

Beilstein J. Org. Chem. 2013, 9, 36–48, doi:10.3762/bjoc.9.5

• converted into 54. Proton loss of this σ-complex yields the isolated aromatic product 57 in the last step. Thermal cyclizations of tetraenes such as 51 to aromatic compounds have been reported in the literature [31]. For the interception of the cations in Scheme 11 by bromide very similar results are

Intramolecular carbolithiation of N-allyl-ynamides: an efficient entry to 1,4-dihydropyridines and pyridines – application to a formal synthesis of sarizotan

• Wafa Gati,
• Mohamed M. Rammah,
• Mohamed B. Rammah and
• Gwilherm Evano

Beilstein J. Org. Chem. 2012, 8, 2214–2222, doi:10.3762/bjoc.8.250

• acidic and oxidative conditions would then afford the highly substituted dihydropyridine or pyridine derivatives 5 and 6, respectively. While there were no examples of such exclusive anionic 6-endo-dig cyclizations reported to the best of our knowledge [39], we felt that the presence of the chelating

The chemistry of bisallenes

• Henning Hopf and
• Georgios Markopoulos

Beilstein J. Org. Chem. 2012, 8, 1936–1998, doi:10.3762/bjoc.8.225

• already oxidized by standing in air; the tetramethyl derivative 24 is stable towards air [139]. 1.4.3 Metal-induced reactions Although metal-initiated reactions (usually cyclizations) have become important ring-forming processes for the “higher” and heteroorganic bisallenes (see Sections 2.3 and 6.2

A quantitative approach to nucleophilic organocatalysis

• Herbert Mayr,
• Sami Lakhdar,
• Biplab Maji and
• Armin R. Ofial

Beilstein J. Org. Chem. 2012, 8, 1458–1478, doi:10.3762/bjoc.8.166

• Herbert Mayr Sami Lakhdar Biplab Maji Armin R. Ofial Department Chemie, Ludwig-Maximilians-Universität München, Butenandstr. 5-13 (Haus F), 81377 München, Germany 10.3762/bjoc.8.166 Abstract The key steps in most organocatalytic cyclizations are the reactions of electrophiles with nucleophiles

Parallel and four-step synthesis of natural-product-inspired scaffolds through modular assembly and divergent cyclization

• Hiroki Oguri,
• Haruki Mizoguchi,
• Hideaki Oikawa,
• Aki Ishiyama,
• Masato Iwatsuki,
• Kazuhiko Otoguro and
• Satoshi Ōmura

Beilstein J. Org. Chem. 2012, 8, 930–940, doi:10.3762/bjoc.8.105

• divergent cyclizations, we have developed a four-step synthetic process to yield a collection of natural-product-inspired scaffolds. Modular assembly of building blocks onto a piperidine-based manifold 6, having a carboxylic acid group, was achieved through Ugi condensation, N-acetoacetylation and

• subsequent installation of a diazoimide group. This allowed three-step access to collections of cyclization precursors with a linkage of the piperidine and the indole units as key substructures shared with naturally occurring alkaloids. Rhodium-catalyzed cyclizations of diazoimides and subsequent divergent

• composed of indole (red) and piperidine (blue) groups; (c) divergent cyclizations to generate scaffold variations as an illustration of the “Build-Couple-Pair” strategy in diversity-oriented synthesis. (a) Synthetic plans based on modular assembly and divergent cyclizations leading to fused skeletons; (b

An intramolecular inverse electron demand Diels–Alder approach to annulated α-carbolines

• Zhiyuan Ma,
• Feng Ni,
• Grace H. C. Woo,
• Sie-Mun Lo,
• Philip M. Roveto,
• Scott E. Schaus and
• John K. Snyder

Beilstein J. Org. Chem. 2012, 8, 829–840, doi:10.3762/bjoc.8.93

• annulations was previously noted by Taylor [95][96][97][98], and has been ascribed to the greater entropy loss for the larger rings [99]. Indeed, it has been estimated that the effective molarity for 5-membered ring closures can be as high as 1,000-fold greater in comparison to 6-membered ring cyclizations

N-Heterocyclic carbene/Brønsted acid cooperative catalysis as a powerful tool in organic synthesis

• Rob De Vreese and
• Matthias D’hooghe

Beilstein J. Org. Chem. 2012, 8, 398–402, doi:10.3762/bjoc.8.43

• -lactam to γ-lactam ring expansions [29][30], aziridine ring openings followed by cyclization with enolates [31], palladium-catalyzed cyclizations [32], cycloadditions [33], multicomponent reactions [34], and even NHC catalysis [35][36]. Nevertheless, the methodology developed by Rovis indisputably