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

• for the oxidative production of valuable intermediates [264][265][266][267][268][269]. The asymmetric oxidation of 3-substituted cyclopentane-1,2-diones 87a–f is an efficient tool in organic synthesis for the preparation of unsymmetrical γ-lactone acids 88a–f with high optical purity and good yields

• (Table 6). These γ-lactone acids are valuable substrates for the synthesis of compounds with potentially useful pharmacological properties, such as homocitrates, alkyl- and aryl-substituted nucleosides [270][271][272]. The reaction starts with an asymmetric epoxidation of the substituted cyclopentane-1,2

Synergistic chiral iminium and palladium catalysis: Highly regio- and enantioselective [3 + 2] annulation reaction of 2-vinylcyclopropanes with enals

• Haipan Zhu,
• Peile Du,
• Jianjun Li,
• Ziyang Liao,
• Guohua Liu,
• Hao Li and
• Wei Wang

Beilstein J. Org. Chem. 2016, 12, 1340–1347, doi:10.3762/bjoc.12.127

• catalytic regio- and enantioselective [3 + 2] annulation process, which offers a new approach to synthetically important heavily functionalized chiral cyclopentane structures 3, bearing at least 3 stereogenic centers in this one-pot operation [77][78]. To test the feasibility of the designed [3 + 2

• , entry 8). It was found that the reaction took place to afford the desired cyclopentane 3a. Encouraged by this result, we carried out further investigations of the co-catalysts promoted process (Table 2). First, we determined the diastereo- and enantioselectivity of the reaction. The 1H NMR of the

Unusual traits of cis and trans-2,3-dibromo-1,1-dimethylindane on the way from 1,1-dimethylindene to 2-bromo-, 3-bromo-, and 2,3-dibromo-1,1-dimethylindene

• Rudolf Knorr,
• David S. Stephenson,
• Ernst Lattke,
• Petra Böhrer and
• Jakob Ruhdorfer

Beilstein J. Org. Chem. 2016, 12, 1178–1184, doi:10.3762/bjoc.12.113

• (no cyclopentane, no benzene), a voluminous precipitate began to emerge slowly at rt within ca. one hour. When this colorless powder of 2-bromo-3-lithio-1,1-dimethylindene (10) had settled after 20 hours at rt, the supernatant was withdrawn by syringe, and the residue was washed with dry pentane (3

Enantioselective carbenoid insertion into C(sp³)–H bonds

• J. V. Santiago and
• A. H. L. Machado

Beilstein J. Org. Chem. 2016, 12, 882–902, doi:10.3762/bjoc.12.87

• reagents, also used as solvent, were cyclopentane, cyclohexane and cycloheptane. Two factors are noteworthy in this work. Unlike the carboxamide complexes (R)-18 and (S)-18 previously reported by Doyle and coworkers (Table 2), where the complexation of the chiral ligand to rhodium atoms occurs through the

Study on the synthesis of the cyclopenta[f]indole core of raputindole A

• Nils Marsch,
• Mario Kock and
• Thomas Lindel

Beilstein J. Org. Chem. 2016, 12, 334–342, doi:10.3762/bjoc.12.36

• quaternary center was to be formed. Ideally, anellation of a cyclopentane would be possible at an indole with an intact enamine partial structure (B, Scheme 1). Such an approach seemed possible, because we had already cyclized 6-prenoylindole to a mixture of cyclopenta[f]- and -[g]indoles in a Nazarov-type

• assemble the cyclopenta[f]indole section present in the natural product raputindole A (1). As long as the cyclopentane ring would not be installed, it was indeed possible to work with 2,3-unsubstituted, N-Boc-protected indoles. In particular, the Mo/Au-catalyzed Meyer–Schuster rearrangement of

• the use of indolines instead of sensitive indoles. Cyclopentane anellation by SnCl4-induced cyclization of phenylvinylcarbinols became possible, at least for the sterically congested β-cyclocitral adduct 40 of N-TIPS-indoline. The less sterically demanding substrate 44 gave lower yields. Experiments

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

• cycloalkanes 2 and N-methyl-N-(2-methylallyl)benzamide (4a). As indicated in Scheme 3, several cycloalkanes were well-tolerated in this radical reaction resulting in the corresponding product. In the case of cyclopentane (2b), a slightly lower chemical yield was obtained (46%, 5ab), while the reactions of

SmI₂-mediated dimerization of indolylbutenones and synthesis of the myxobacterial natural product indiacen B

• Nils Marsch,
• Peter G. Jones and
• Thomas Lindel

Beilstein J. Org. Chem. 2015, 11, 1700–1706, doi:10.3762/bjoc.11.184

• and Meyer–Schuster rearrangement 6-prenoylindole was synthesized and reductively dimerized to a cyclopentane in a [3 + 2] cycloaddition by treatment with SmI2 in THF. From 4-iodoindole, the natural product indiacen B from the myxobacterium Sandaracinus amylolyticus was synthesized for the first time

• be too distant from each other to show an nOe. In any cyclopentane conformation this would be the case for hydrogen atoms located in 1,3-trans-position. Thus, the presence of a NOESY cross peak would exclude 1,3-trans-orientation of the respective hydrogens. In diastereomers 6, 7, and 8 there were

• , exclusive trans-arrangement of aryl substituents at the cyclopentane ring had been observed [21][22][23][24]. Aryl substituents generally prefer the antiperiplanar arrangement, as observed by Zhou and Zhang, who reductively dimerized chalcone derivatives to trans-diarylated cyclopentanols [23]. Cis isomers

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

Synthesis of novel N-cyclopentenyl-lactams using the Aubé reaction

• Madhuri V. Shinde,
• Rohini S. Ople,
• Ekta Sangtani,
• Rajesh Gonnade and
• D. Srinivasa Reddy

Beilstein J. Org. Chem. 2015, 11, 1060–1067, doi:10.3762/bjoc.11.119

• , based on an allyl–azide rearrangement, we obtained lactams with an 1,2-substituted cyclopentane on the nitrogen instead. These compounds can be useful tools as they are structurally close to nucleosides and may have pharmaceutical relevance. Experimental General procedure for the Aubé reaction using BF3

Microsolvation and sp²-stereoinversion of monomeric α-(2,6-di-tert-butylphenyl)vinyllithium as measured by NMR

• Rudolf Knorr,
• Monika Knittl and
• Eva C. Rossmann

Beilstein J. Org. Chem. 2014, 10, 2521–2530, doi:10.3762/bjoc.10.263

• properties of 4 The Br/Li interchange reaction (Scheme 2) between n-BuLi and the bromoalkene [14] 3 that generates the title compound α-(2,6-di-tert-butylphenyl)vinyllithium (4) in cyclopentane as the solvent was almost finished after 70 min at room temperature (rt), affording 1-bromobutane (n-BuBr), the

• cyclopentane solution of 5 and n-BuLi did not react during several days at rt; on addition of TMEDA (ca. 3–5 equiv), however, merely one quickly recorded 1H NMR spectrum could be taken before crystals of 4&TMEDA began to precipitate. Surplus n-BuLi converted the coproduct n-BuSnMe3 into n-Bu2SnMe2 (and

• until NMR spectra could be measured. In such a colorless solution of 4&TMEDA in THF/cyclopentane (ca. 83:17 by volume), THF had displaced TMEDA from its coordination to 4; at below −50 °C, the olefinic proton resonances of 4 (Table S2, [15]) displayed a well resolved AB spectral system (two doublets

Regio- and stereoselective synthesis of new diaminocyclopentanols

• Evgeni A. Larin,
• Valeri S. Kochubei and
• Yuri M. Atroshchenko

Beilstein J. Org. Chem. 2014, 10, 2513–2520, doi:10.3762/bjoc.10.262

• crucial for the reaction outcome. Thus, treatment of (1RS,2SR,3SR)-1,2-epoxy-3-(N,N-dibenzylamino)cyclopentane (3b) with amines gave a mixture of C1 and C2 regioadducts, while the use of (1RS,2SR,3SR)-1,2-epoxy-3-(N-benzyl-N-methylamino)cyclopentane (3a) led ultimately to C1 adducts. Base-catalyzed

• subsequent oxirane ring opening represent a viable approach for the development of new pharmaceutically relevant scaffolds. As a part of our ongoing research in the development of new aminocyclitols, we exploited cyclopentane derivatives to mimic both the 2-deoxystreptamine ring, a core component in

Application of cyclic phosphonamide reagents in the total synthesis of natural products and biologically active molecules

• Thilo Focken and
• Stephen Hanessian

Beilstein J. Org. Chem. 2014, 10, 1848–1877, doi:10.3762/bjoc.10.195

• subunit (Figure 8) [116][117][118]. The first total synthesis of nudiflosides A and D was achieved by Hanessian and co-workers, which aimed at confirming their proposed structural and stereochemical assignment (Scheme 19) [49]. The correct installation of the stereocenters of the cyclopentane subunit 159

• group. Final removal of the TBDPS protecting group gave cyclopentane triol 159, which was esterified with varying equivalents of oleoside monomethyl ester peracetate 160 under Yamaguchi conditions [119][120] to give nudiflosides A (151) and D (13), respectively, thereby completing the synthesis and

Structure/affinity studies in the bicyclo-DNA series: Synthesis and properties of oligonucleotides containing bc^en-T and iso-tricyclo-T nucleosides

• Branislav Dugovic,
• Michael Wagner and
• Christian J. Leumann

Beilstein J. Org. Chem. 2014, 10, 1840–1847, doi:10.3762/bjoc.10.194

• in both nucleosides the furanose unit appears in an almost perfect 2’-endo conformation giving rise to a trans arrangement of torsion angle δ (O3’–C3’–C4’–C5’). In both structures the cyclopentane ring exists in a shallow envelope conformation with C5’ being slightly out of plane. This leads to a

• the conformation of the bicyclic ring system. A comparison of 8β and 11β with bc-T, having a saturated cyclopentane unit clearly reveals structural differences. The largest deviation is associated with the position of the 5’-OH group which is in a pseudoequatorial orientation in bc-T, giving rise to a

Stereoselective synthesis of carbocyclic analogues of the nucleoside Q precursor (PreQ₀)

• Sabin Llona-Minguez and
• Simon P. Mackay

Beilstein J. Org. Chem. 2014, 10, 1333–1338, doi:10.3762/bjoc.10.135

• -substituted analogues with interesting three-dimensional character, including chiral cyclopentane-1,2-diol and -1,2,3-triol derivatives. This unusual substitution pattern provides a useful starting point for the discovery of novel bioactive molecules. Keywords: diol synthesis; nucleoside; PreQ0

• -position of the heterocyclic core (systematic numbering) are scarce in the chemical literature and the methods available generally lack experimental information, making them unsatisfactory [18][19][20][21][22][23][24][25]. Inspired by the cyclopentane-1,2,3-triol motif present in noraristeromycin 5 (Figure

Cyclization–endoperoxidation cascade reactions of dienes mediated by a pyrylium photoredox catalyst

• Nathan J. Gesmundo and
• David A. Nicewicz

Beilstein J. Org. Chem. 2014, 10, 1272–1281, doi:10.3762/bjoc.10.128

• step is irrelevant, whereas the opposite scenario involving a benzylic radical intermediate would require a stereospecific addition of oxygen to the same face of the cyclopentane system as the isoprenyl cation in order for endoperoxide formation to occur. With optimized conditions identified, we sought

Synthesis of complex intermediates for the study of a dehydratase from borrelidin biosynthesis

• Frank Hahn,
• Nadine Kandziora,
• Steffen Friedrich and
• Peter F. Leadlay

Beilstein J. Org. Chem. 2014, 10, 634–640, doi:10.3762/bjoc.10.55

• , anticancer and anti-angiogenesis activities, which are probably caused by the inhibition of threonyl-tRNA synthetase and apoptosis induction by caspase activation [1][2][3][4]. It bears several unusual structural elements like a cyclopentane ring and a carbonitrile (Figure 1a), which are built-up by

Iron-catalyzed decarboxylative alkenylation of cycloalkanes with arylvinyl carboxylic acids via a radical process

• Jincan Zhao,
• Hong Fang,
• Jianlin Han and
• Yi Pan

Beilstein J. Org. Chem. 2013, 9, 1718–1723, doi:10.3762/bjoc.9.197

• the product 3p in 89% yield. In general, the stereoselectivity of this reaction was excellent and only trans-isomers were obtained in all cases. Next, other cycloalkanes, including cyclopentane, cycloheptane and cyclooctane, were reacted with different cinnamic acids 1, giving products 4a–f in 83–95

The preparation of several 1,2,3,4,5-functionalized cyclopentane derivatives

• André S. Kelch,
• Peter G. Jones,
• Ina Dix and
• Henning Hopf

Beilstein J. Org. Chem. 2013, 9, 1705–1712, doi:10.3762/bjoc.9.195

• with various bromination reagents. Whenever possible we confirm the structures of intermediate compounds or byproducts by X-ray structural analysis. Results and Discussion cis,cis,cis,cis-1,2,3,4,5-Pentakis(hydroxymethyl)cyclopentane (16) and derivatives The pentaalcohol 16 is a known compound, having

• the Supporting Information File 1. cis,cis,cis,trans-1,2,3,4,5- (26), cis,cis,trans,cis-1,2,3,4,5-Pentakis(methoxycarbonyl)cyclopentane (27) and several of their derivatives For the other two routes to precursors of [5]radialene (3) discussed here, the ten carbon atoms of the desired final product

• ; ellipsoids represent 30% probability levels. Structure of 32 in the crystal; ellipsoids represent 50% probability levels. The first members of the [n]radialene series and retrosynthesis for [5]radialene (3). Preparation of cis,cis,cis,cis-1,2,3,4,5-pentakis(hydroxymethyl)cyclopentane (16) according to

Substituent effect on the energy barrier for σ-bond formation from π-single-bonded species, singlet 2,2-dialkoxycyclopentane-1,3-diyls

• Jianhuai Ye,
• Yoshihisa Fujiwara and
• Manabu Abe

Beilstein J. Org. Chem. 2013, 9, 925–933, doi:10.3762/bjoc.9.106

• and cyclopentane-1,3-diyls. Experimental investigation of the chemistry of singlet diradicals has become possible. The present study explores the substituents and the effect of their substitution pattern at the C(1)–C(3) positions on the lifetime of singlet octahydropentalene-1,3-diyls to understand

• -diyls [4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20] and cyclopentane-1,3-diyls [17][21][22][23][24][25][26]. Detailed experimental study of singlet diradical chemistry is thus now possible using the long-lived localized singlet diradicals. So far, we have studied singlet diradical

• , 702; UV (MTHF) λmax 365 (ε 106.7); 1H NMR (500 MHz, C6D6) δ 1.20–1.75 (m, 6H), 3.69 (t, J = 5.13 Hz, 2H), 4.15 (s, 2H), 4.29 (s, 2H), 6.90–8.19 (m, 20H, overlapping with C6H6); 13C NMR (125 MHz, C6D6) δ 25.96 (t, CH2, cyclopentane), 28.16 (t, CH2, cyclopentane), 49.27 (d, CH, cyclopentane), 66.16 (t

Some aspects of radical chemistry in the assembly of complex molecular architectures

• Béatrice Quiclet-Sire and
• Samir Z. Zard

Beilstein J. Org. Chem. 2013, 9, 557–576, doi:10.3762/bjoc.9.61

• addition to phenyl vinyl sulfone and closure to form the cyclopentane ring in 19, and then by a second intermolecular addition to phenyl vinyl sulfone to furnish radical 20, which finally evolves into the observed product 21 by transfer of the pyridylthiyl group from the starting Barton ester 16. Even

Synthesis of spiro[dihydropyridine-oxindoles] via three-component reaction of arylamine, isatin and cyclopentane-1,3-dione

• Yan Sun,
• Jing Sun and
• Chao-Guo Yan

Beilstein J. Org. Chem. 2013, 9, 8–14, doi:10.3762/bjoc.9.2

• -component reactions of arylamine, isatin and cyclopentane-1,3-dione in acetic acid at room temperature. On the other hand the condensation of isatin with two equivalents of cyclopentane-1,3-dione gave 3,3-bis(2-hydroxy-5-oxo-cyclopent-1-enyl)oxindole in high yields. The reaction mechanism and substrate

• three-component reaction of arylamine, isatin and cyclopentane-1,3-dione. Results and Discussion Recently we found that the four-component reactions of arylamine, acetylenedicarboxylate, isatin and dimedone in acetic acid resulted in the novel functionalized tetrahydrospiro[indoline-3,2’-quinoline

• -5-methylisatin and cyclopentane-1,3-dione in acetic acid was carried out at room temperature. After workup, we were a little surprised to find that there was no unit of acetylenedicarboxylate in the obtained product (Scheme 1b). In another experiment, the three-component reaction of isatin

Features of the behavior of 4-amino-5-carboxamido-1,2,3-triazole in multicomponent heterocyclizations with carbonyl compounds

• Eugene S. Gladkov,
• Katerina A. Gura,
• Svetlana M. Sirko,
• Sergey M. Desenko,
• Ulrich Groth and
• Valentin A. Chebanov

Beilstein J. Org. Chem. 2012, 8, 2100–2105, doi:10.3762/bjoc.8.236

• '-cyclopentane}-3-carboxamide (4a) or 5,6,7,8-tetrahydro-4H-spiro{[1,2,3]triazolo[5,1-b]quinazoline-9,1'-cyclohexane}-3-carboxamide (4b) under all the conditions tested. The best results were observed in the case of microwave-assisted synthesis in methanol at 120 °C. Spirocompound 4c may be obtained by a

Tricyclic flavonoids with 1,3-dithiolium substructure

• Lucian G. Bahrin,
• Peter G. Jones and
• Henning Hopf

Beilstein J. Org. Chem. 2012, 8, 1999–2003, doi:10.3762/bjoc.8.226

• led to the synthesis of derivative 1, a selective estrogen receptor β agonist (SERBA-1, Figure 1) [5]. Studies that focus on the structure–activity relationship were reported [6][7]. It was shown that a cyclopentane ring at the 3,4-carbon positions (labeled C, Figure 1) leads to a substantial rise in

The chemistry of bisallenes

• Henning Hopf and
• Georgios Markopoulos

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

Stereoselective synthesis of trans-fused iridoid lactones and their identification in the parasitoid wasp Alloxysta victrix, Part I: Dihydronepetalactones

• Nicole Zimmermann,
• Robert Hilgraf,
• Lutz Lehmann,
• Daniel Ibarra and
• Wittko Francke

Beilstein J. Org. Chem. 2012, 8, 1246–1255, doi:10.3762/bjoc.8.140

• ]. Similar results of highly stereoselective hydroborations of structurally related chiral cyclopentene derivatives have been reported [20][21]. Synthesis of trans,trans-dihydronepetalactone b To install a trans,trans-configuration between the substituents at C5-C1 and C1-C2 of the cyclopentane backbone

• synthesis of the cis,trans dihydronepetalactone c, a cis,trans-configuration between the substituents at C5-C1 and C1-C2 of the cyclopentane backbone needed to be established. With acetate 16 as the key intermediate, a stereoselective “syn”-addition of hydrogen from the same side as the (R)-configured side