Sugar-derived oxazolone pseudotetrapeptide as γ-turn inducer and anion-selective transporter

• Sachin S. Burade,
• Sushil V. Pawar,
• Tanmoy Saha,
• Navanath Kumbhar,
• Amol S. Kotmale,
• Manzoor Ahmad,
• Pinaki Talukdar and
• Dilip D. Dhavale

Beilstein J. Org. Chem. 2019, 15, 2419–2427, doi:10.3762/bjoc.15.234

• conformation [5]. Amongst these, the use of sugar-derived TAAs in peptidomimetics is less explored. The linear tri-/tetrapeptides and spiro-peptides at the anomeric position of mannofructose are known [6][7][8]. Stick and co-workers have reported the synthesis of tetrasubstituted sugar furanoid amino acid

Recent advances in transition-metal-catalyzed incorporation of fluorine-containing groups

• Xiaowei Li,
• Xiaolin Shi,
• Xiangqian Li and
• Dayong Shi

Beilstein J. Org. Chem. 2019, 15, 2213–2270, doi:10.3762/bjoc.15.218

• co-workers [71] described the one-pot asymmetric gem-chlorofluorination of active methylene compounds by using a copper(II) complex with a chiral spiro 2-pyridyl monooxazoline ligand (SPYMOX). The corresponding α-chloro-α-fluoro-β-keto esters were isolated with up to 92% ee (Scheme 29a). This

Synthesis of 1-azaspiro[4.4]nonan-1-oxyls via intramolecular 1,3-dipolar cycloaddition

• Yulia V. Khoroshunova,
• Denis A. Morozov,
• Andrey I. Taratayko,
• Polina D. Gladkikh,
• Yuri I. Glazachev and
• Igor A. Kirilyuk

Beilstein J. Org. Chem. 2019, 15, 2036–2042, doi:10.3762/bjoc.15.200

• effect may be useful for structural studies by means of PELDOR or DQC [5]. We recently reported the synthesis of sterically shielded pyrrolidine nitroxide 1 via a stereospecific consecutive assembly of two spiro-(2-hydroxymethyl)cyclopentane moieties. These procedures included the addition of pent-4

• with only one spiro(2-hydroxymethyl)cyclopentane moiety. The rates of reduction of the new nitroxides with ascorbate were measured. Results and Discussion Aldonitrones 5b,c were prepared similarly to the well-known synthesis of 5,5-dimethyl-1-pyrroline-1-oxide (DMPO, 5a) [9][10] from nitrocyclohexane

• performed for reductive isoxazolidine ring opening [15][16] producing aminoalcohols 9a–c in 85–95% yields (Scheme 2). We have previously reported that oxidation of secondary amines with a spiro(2-hydroxymethyl)cyclopentane moiety at the α-carbon with the H2O2/WO42− system is ineffective whereas conversion

Design of a double-decker coordination cage revisited to make new cages and exemplify ligand isomerism

• Sagarika Samantray,
• Sreenivasulu Bandi and
• Dillip K. Chand

Beilstein J. Org. Chem. 2019, 15, 1129–1140, doi:10.3762/bjoc.15.109

• formation of PdL2-type spiro and Pd3L4-type double-decker complexes that is reversible under appropriate conditions. Subsequently, other research groups (Chand, Clever, Crowley and Yoshizawa groups) published Pd3L4-type cages [24]. This design has been further explored by Crowley et al. for the synthesis of

Multicomponent reactions (MCRs): a useful access to the synthesis of benzo-fused γ-lactams

• Edorta Martínez de Marigorta,
• Jesús M. de Los Santos,
• Ana M. Ochoa de Retana,
• Javier Vicario and
• Francisco Palacios

Beilstein J. Org. Chem. 2019, 15, 1065–1085, doi:10.3762/bjoc.15.104

• . This is a good partner for a cycloaddition with an imine such as 99 that would give rise to the spiro β- and γ-lactam derivative 101 in a diastereoselective manner. Indeed, a seminal contribution also made use of a similar Pd-catalysed carbonylation followed by amide formation and cyclization in a

Novel (2-amino-4-arylimidazolyl)propanoic acids and pyrrolo[1,2-c]imidazoles via the domino reactions of 2-amino-4-arylimidazoles with carbonyl and methylene active compounds

• Victoria V. Lipson,
• Tetiana L. Pavlovska,
• Nataliya V. Svetlichnaya,
• Anna A. Poryvai,
• Nikolay Yu. Gorobets,
• Erik V. Van der Eycken,
• Irina S. Konovalova,
• Svetlana V. Shiskina,
• Alexander V. Borisov,
• Vladimir I. Musatov and
• Alexander V. Mazepa

Beilstein J. Org. Chem. 2019, 15, 1032–1045, doi:10.3762/bjoc.15.101

• -arylpropanoic acids. The interaction of 2-amino-4-arylimidazoles with aromatic aldehydes or isatins and acyclic methylene active compounds has led to the formation of pyrrolo[1,2-c]imidazole-6-carbonitriles, pyrrolo[1,2-с]imidazole-6-carboxylates and spiro[indoline-3,7'-pyrrolo[1,2-c]imidazoles], which can be

• of Leucetta Sp. and Clathrina Sp. are presented by achiral imidazole alkaloids from the group of benzyl substituted 2-aminoimidazole (dorimidazole A (I), naamine A (II)), fused cyclic systems (2-amino-2-deoxykealiiquinone (III)) and spiro-linked compounds ((−)-spirocalcaridine B (IV)) [2]. Agelas Sp

• . Aeruginosa [22][23]. We have used 4-aryl-substituted 2-aminoimidazoles described by the authors of the aforementioned works as polyfunctional building blocks for the formation of different fused and spiro-linked heterocyclic systems. Last ones are able to act as precursors in the synthesis of the substances

Annulation of 1H-pyrrole-2,3-diones by thioacetamide: an approach to 5-azaisatins

• Aleksandr I. Kobelev,
• Ekaterina E. Stepanova,
• Maksim V. Dmitriev and
• Andrey N. Maslivets

Beilstein J. Org. Chem. 2019, 15, 364–370, doi:10.3762/bjoc.15.32

• and Discussion Previously, we reported an efficient catalyst-free synthesis of spiro[thiazolo-5,2'-pyrroles] 1 via interaction of pyrrolobenzoxazinetriones (PBTs) 2 with thiobenzamide (Scheme 2) [17][18]. In continuation of this research [17][18], and in order to extend the scope of the reaction, we

• attempted to involve the simplest aliphatic thioamide, thioacetamide, in the interaction with PBTs 2. As a result, we obtained the expected spiro[thiazolo-5,2'-pyrroles] 3, which were found to exist in a form with an exo-methylene group according to the NMR spectra (Scheme 3) [19]. Unfortunately, the

• addition of water did not affect the yield of compound 4a or even slightly lowered it. Having determined the optimal conditions of the reactions, we turned our attention to the main distinction of the proposed pathways of formation of compounds 4 – the particle that interacted with the spiro[thiazolo-5,2

An overview on recent advances in the synthesis of sulfonated organic materials, sulfonated silica materials, and sulfonated carbon materials and their catalytic applications in chemical processes

• Hashem Sharghi,
• Pezhman Shiri and
• Mahdi Aberi

Beilstein J. Org. Chem. 2018, 14, 2745–2770, doi:10.3762/bjoc.14.253

• these catalysts for extensive reactions, including the synthesis of bis(indolyl)methane derivatives, β-amino carbonyl compounds, 14H-dibenzo[a,j]xanthene derivatives, 1,8-dioxodecahydroacridine derivatives, xanthene derivatives, pyrimido[4,5-b]quinoline derivatives, spiro-isatin derivatives, spiro

• -sulfo-1,4-diazabicyclo[2.2.2]octane-1,4-diium) chloride (C4(DABCO-SO3H)2·4Cl, 31) and its applications in the synthesis of spiro-oxindole derivatives 36 and 37 was described. C4(DABCO-SO3H)2·4Cl 31 acted as an efficient, cheap, and reusable nanocatalyst for synthesis of 2-amino-4H-pyran derivatives 36

• ), and 1-naphthol (34d)), and malononitrile (35) in water at 90 °C. Isatin (32) and acenaphthenequinone (33) were reacted with C–H activated acids 20a,b, 23, and 34a–c and malononitrile (35) to form the corresponding spiro-isatin derivatives 36 and spiro-acenaphthenequinone derivatives 37 under mild and

Assembly of fully substituted triazolochromenes via a novel multicomponent reaction or mechanochemical synthesis

• Robby Vroemans,
• Yenthel Verhaegen,
• My Tran Thi Dieu and
• Wim Dehaen

Beilstein J. Org. Chem. 2018, 14, 2689–2697, doi:10.3762/bjoc.14.246

• , which enables them to undergo a high variety of reactions and functionalizations [15]. Combining the chromene core with the 1,2,3-triazole structural motif has led to some interesting new molecules [16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31]. Very recently, spiro-fused

Design and synthesis of C₃-symmetric molecules bearing propellane moieties via cyclotrimerization and a ring-closing metathesis sequence

• Sambasivarao Kotha,
• Saidulu Todeti and
• Vikas R. Aswar

Beilstein J. Org. Chem. 2018, 14, 2537–2544, doi:10.3762/bjoc.14.230

• ) reaction [11][12], and rearrangement of spiro-ketones, nucleophilic substitutions of alkenes, and photochemical addition reactions. Multicomponent reactions (MCRs) are also used for the synthesis of hetero-propellanes [13][14]. Recently, heterocyclic propellanes have been reviewed [15][16]. Our group also

Synergistic approach to polycycles through Suzuki–Miyaura cross coupling and metathesis as key steps

• Sambasivarao Kotha,
• Milind Meshram and
• Chandravathi Chakkapalli

Beilstein J. Org. Chem. 2018, 14, 2468–2481, doi:10.3762/bjoc.14.223

• %). Finally, the spiro compound 30 was subjected to the SM coupling using two different boronic acids to produce the aryl substituted spiro compounds such as 31 (96%) and 32 (79%) (Scheme 4). Along similar lines, we have also demonstrated the synthesis of bis-spirocycles such as 37 by adopting a double RCM

• product 35 was subjected to SM coupling using phenylboronic acid (36) to afford the cross-coupling product 37 (97%, Scheme 5). In another instance, a simple synthetic approach to spiro-fluorene derivative 41 was described involving a serial usage of RCM and SM coupling [37]. To this end, bromofluorene 38

D-Fructose-based spiro-fused PHOX ligands: synthesis and application in enantioselective allylic alkylation

• Michael R. Imrich,
• Jochen Kraft,
• Cäcilia Maichle-Mössmer and
• Thomas Ziegler

Beilstein J. Org. Chem. 2018, 14, 2082–2089, doi:10.3762/bjoc.14.182

• .14.182 Abstract Phosphinooxazoline (PHOX) ligands are an important class of ligands in asymmetric catalysis. We synthesized ten novel D-fructose-derived spiro-fused PHOX ligands with different steric and electronic demand. The application of two of them was tested in asymmetric allylic alkylation. The

• pyridyloxazoline (PyOx) ligands in which the sugar moiety was linked to pyridine via an annulated oxazoline, 3, as well as via a spiro-fused oxazoline, 4. We found that the spiro-fused ligands gave higher enantioselectivities (up to 93% ee) than the annulated ligands (up to 66% ee) in allylic substitution [20][21

• ][22]. This led us to extend the concept of spiro-fused carbohydrate oxazolines for asymmetric synthesis by developing new types of carbohydrate-based PHOX ligands. Herein, we present ten novel spiro-PHOX ligands containing diphenylphosphino groups, 5, which can be synthesized in four to six steps

Synthesis of new tricyclic 5,6-dihydro-4H-benzo[b][1,2,4]triazolo[1,5-d][1,4]diazepine derivatives by [3⁺ + 2]-cycloaddition/rearrangement reactions

• Lin-bo Luan,
• Zi-jie Song,
• Zhi-ming Li and
• Quan-rui Wang

Beilstein J. Org. Chem. 2018, 14, 1826–1833, doi:10.3762/bjoc.14.155

• followed by a ring-expansion rearrangement. In the rearrangement reaction, the phenyl substituent in the initially formed spiro-triazolium adducts 16 underwent a [1,2]-migration from C(3) to the electron-deficient N(2). This led to the ring expansion from 6-membered piperidine to 7-membered diazepine

• cannot be isolated by now [31]. Then, the nitrogen atom of the nitrile approaches to the central electron-deficient carbon atom in 14 to form a Ritter-type nitrilium salt 15 [48]. Salt 15 then undergoes a concerted but asynchronous cyclization [49] to afford the initial spiro-substituted adduct 16, which

Synthesis of spirocyclic scaffolds using hypervalent iodine reagents

• Fateh V. Singh,
• Priyanka B. Kole,
• Saeesh R. Mangaonkar and
• Samata E. Shetgaonkar

Beilstein J. Org. Chem. 2018, 14, 1778–1805, doi:10.3762/bjoc.14.152

• functionalized benzocoumarins to spirocyclic lactones. In 2015, Du and co-workers [74] reported a spirocyclization of diarylacetylenes to fused spiro polycyclic compounds through a hypervalent iodine-mediated cascade annulation reaction. In this reaction, the Lewis acid BF3·Et2O acts as catalyst which activates

• ) in presence of 3.0 equivalents of TFA as an additive in dichloromethane (Scheme 17). The fused tricyclic compound 53 was obtained as major product in 55% yield along with the spiro compound 54 as a minor product in 8% yield. In 2009, Zhang and co-workers [89] reported an efficient method for the

• synthesis of spiro β-lactams via oxidative dearomatization reactions. In this report, the synthesis of spiro β-lactams 56 were achieved successfully by the oxidative cyclization of p-substituted phenols 55 using PIDA (15) as an electrophile and copper(II) sulfate pentahydrate as an additive in the presence

β-Hydroxy sulfides and their syntheses

• Mokgethwa B. Marakalala,
• Edwin M. Mmutlane and
• Henok H. Kinfe

Beilstein J. Org. Chem. 2018, 14, 1668–1692, doi:10.3762/bjoc.14.143

• -epoxides, 2,3-epoxyalcohols as well as their OTMS, OTs and OPh derivatives. Reactions of 1-oxa-spiro[2.5]octane and 2-phenyloxirane (styrene oxide) with thiophenol both gave near quantitative yields of the hydroxy sulfides, with substitution occurring nearly exclusively at the sterically less hindered β

Recent advances in phosphorescent platinum complexes for organic light-emitting diodes

• Cristina Cebrián and
• Matteo Mauro

Beilstein J. Org. Chem. 2018, 14, 1459–1481, doi:10.3762/bjoc.14.124

Methyl isocyanide as a convertible functional group for the synthesis of spirocyclic oxindole γ-lactams via post-Ugi-4CR/transamidation/cyclization in a one-pot, three-step sequence

• Amarendar Reddy Maddirala and
• Peter R. Andreana

Beilstein J. Org. Chem. 2018, 14, 875–883, doi:10.3762/bjoc.14.74

• Amarendar Reddy Maddirala Peter R. Andreana Department of Chemistry and Biochemistry and School of Green Chemistry and Engineering, University of Toledo, 2801 W. Bancroft Street, Toledo, OH 43606, USA 10.3762/bjoc.14.74 Abstract The synthesis of spiro[indoline-3,2'-pyrrole]-2,5'(1'H)-diones and

• spiro[indoline-3,2'-pyrrolidine]-2,5'-diones, via a post-Ugi-domino transamidation/cyclization sequential process, has been achieved in three sequential steps utilizing a one-pot reaction protocol. The variation in carboxylic acid substrates allows for the generation of new chiral racemic quaternary

• synthetic method for these molecules that allows for structural diversity is also important but not necessarily trivial. For these and other reasons, we became interested in synthesizing spiro[indoline-3,2'-pyrrole]-2,5'(1'H)-dione and spiro[indoline-3,2'-pyrrolidine]-2,5'-dione scaffolds (a class of

Mannich base-connected syntheses mediated by ortho-quinone methides

• Petra Barta,
• Ferenc Fülöp and
• István Szatmári

Beilstein J. Org. Chem. 2018, 14, 560–575, doi:10.3762/bjoc.14.43

• are also known to undergo oligomerization in the absence of dienophiles and nucleophiles via an oxo-Diels–Alder protocol (Table 4). During the syntheses of 1,4,9,10-anthradiquinones with potential antitumor activity, Kucklaender et al. isolated new spiro derivatives 38 [77]. These latter spirocyclic

One-pot preparation of 4-aryl-3-bromocoumarins from 4-aryl-2-propynoic acids with diaryliodonium salts, TBAB, and Na₂S₂O₈

• Teppei Sasaki,
• Katsuhiko Moriyama and
• Hideo Togo

Beilstein J. Org. Chem. 2018, 14, 345–353, doi:10.3762/bjoc.14.22

• -alkynoates with N-bromosuccinimide (NBS) at rt [34], where those reactions proceed via radical spiro-cyclization and then radical 1,2-carboxyl group migration, were reported. On the other hand, diaryliodonium salts are very useful for the C-arylation of active CH groups, the O-arylation of OH groups, and the

• occurs to form aryl 3-aryl-2-propynoate 2 (1st step). The bromocyclization of aryl 3-aryl-2-propynoate 2 with TBAB and Na2S2O8 proceeds via a bromoradical addition to the triple bond to form very reactive vinyl radical I [47]. Ipso-cyclization of the vinyl radical I occurs to form spiro radical

• intermediate II. Then, β-cleavage of the spiro radical intermediate II proceeds to form carboxyl radical III. 6-Exo-trig cyclization of the carboxyl radical III onto the aromatic ring takes place to form adduct radical IV, which would be rapidly oxidized by Na2S2O8 to form cation intermediate V. Smooth

Recent advances on organic blue thermally activated delayed fluorescence (TADF) emitters for organic light-emitting diodes (OLEDs)

• Thanh-Tuân Bui,
• Fabrice Goubard,
• Malika Ibrahim-Ouali,
• Didier Gigmes and
• Frédéric Dumur

Beilstein J. Org. Chem. 2018, 14, 282–308, doi:10.3762/bjoc.14.18

• % could be attained for the sky-blue B4-based devices. Still based on the combination of acridan and 10H-phenoxaborin units, a complete isolation of the two units could be realized in B6 by directly functionalizing the 10H-phenoxaborin core with a spiro-type acridan group [38]. Using this strategy, pure

5-Aminopyrazole as precursor in design and synthesis of fused pyrazoloazines

• Ranjana Aggarwal and
• Suresh Kumar

Beilstein J. Org. Chem. 2018, 14, 203–242, doi:10.3762/bjoc.14.15

• product 4,5-dihydro-1H-pyrazolo[3,4-b]pyridine-6(7H)-one 53 was formed due to C–O bond cleavage from cyclic ester 51. Bazgir et al. [56] described the synthesis of spiro[indoline-3,4'-pyrazolo[3,4-b]pyridine]-2,6'(1'H)-diones 55 by an efficient three-component procedure from the reaction of 5

• described the construction of spiro[indoline-3,4'-pyrazolo[3,4-b]pyridine] derivatives 57 from the multicomponent reaction of 5-amino-3-hydroxy-1-phenyl-1H-pyrazole (46), ketones 56 and isatin 54 in water/acetic acid (3:1) at 90 °C (Scheme 12). Quiroga et al. [58] reported the synthesis of the pyrazolo[3,4

Regiodivergent condensation of 5-alkoxycarbonyl-1H-pyrrol-2,3-diones with cyclic ketazinones en route to spirocyclic scaffolds

• Alexey Yu. Dubovtsev,
• Maksim V. Dmitriev,
• Аndrey N. Maslivets and
• Michael Rubin

Beilstein J. Org. Chem. 2017, 13, 2179–2185, doi:10.3762/bjoc.13.218

• ; spiro compounds; synthetic methods; Introduction Molecular structures based on partially or exhaustively hydrogenated indole and benzofuran cores are omnipresent in nature. Both types of ring systems are found in a variety of important biologically active natural products [1][2][3][4][5][6][7][8][9][10

• spirocondensation of 5-alkoxycarbonyl-1H-pyrrole-2,3-diones (serving as 1,2-bis-electrophiles) with cyclic ketazinones (serving as either 1,3-C,N- or 1,3-C,O-bis-nucleophiles). Results and Discussion Previously, we demonstrated a convenient approach towards spiro[indole-3,2’-pyrroles] 3 based on catalyst-free

• in tautomeric form 18 (Scheme 5). Surprisingly, an alternative direction of spirocyclization involving the reaction of tautomeric form 19 and affording lactam rings proceeded exclusively. The corresponding spiro[indole-3,2’-pyrroles] 21 were obtained exclusively in good yields (Scheme 5). The

Enzymatic separation of epimeric 4-C-hydroxymethylated furanosugars: Synthesis of bicyclic nucleosides

• Neha Rana,
• Manish Kumar,
• Vinod Khatri,
• Jyotirmoy Maity and
• Ashok K. Prasad

Beilstein J. Org. Chem. 2017, 13, 2078–2086, doi:10.3762/bjoc.13.205

• , which is a key precursor for the synthesis of different types of bicyclic/spiro nucleosides, led to the formation of an inseparable 1:1 mixture of the desired product and 4-C-hydroxymethyl-1,2-O-isopropylidene-α-D-xylofuranose. A convenient environment friendly Novozyme®-435 catalyzed selective

Chiral phase-transfer catalysis in the asymmetric α-heterofunctionalization of prochiral nucleophiles

• Johannes Schörgenhumer,
• Maximilian Tiffner and
• Mario Waser

Beilstein J. Org. Chem. 2017, 13, 1753–1769, doi:10.3762/bjoc.13.170

• -workers demonstrated the potential of asymmetric cation-based phase-transfer catalysis to control the absolute configuration of the newly-installed stereogenic centre in this rearrangement reaction [141]. By using their spiro-quaternary ammonium salt catalyst B5 they were able to control the Neber

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

• combination of heterogeneous polymer-supported bi-metallic platinum/iridium alloyed nanoclusters and 5,5’,6,6’-tetrahydroxy-3,3,3’,3’-tetramethyl-1,1’-spiro-bisindane (TTSBI) facilitated a one-pot condensation and oxidative dehydrogenation of o-aminobenzylamine to generate quinazoline derivatives 79 under

• dehydrogenation of tetrahydroisoquinolines. Ruthenium-catalyzed polycyclic heteroarenes. Plausible mechanism of the ruthenium-catalyzed dehydrogenation. Bi-metallic platinum/iridium alloyed nanoclusters and 5,5’,6,6’-tetrahydroxy-3,3,3’,3’-tetramethyl-1,1’-spiro-bisindane (TTSBI) for the synthesis of quinazolines