Glycosylation reactions mediated by hypervalent iodine: application to the synthesis of nucleosides and carbohydrates

• Yuichi Yoshimura,
• Hideaki Wakamatsu,
• Yoshihiro Natori,
• Yukako Saito and
• Noriaki Minakawa

Beilstein J. Org. Chem. 2018, 14, 1595–1618, doi:10.3762/bjoc.14.137

• reaction of trans-cyclobutane sulfoxide 59. The authors concluded that the stereochemistry of the sulfoxide and the nature of the protecting groups had no significant effect on the yield of the Pummerer-type glycosylation [47] (Scheme 8). Pummerer-type glycosylation, which was developed by our group

Stepwise radical cation Diels–Alder reaction via multiple pathways

• Ryo Shimizu,
• Yohei Okada and
• Kazuhiro Chiba

Beilstein J. Org. Chem. 2018, 14, 704–708, doi:10.3762/bjoc.14.59

• from the cyclobutane 5 (Scheme 6). We also found that the Diels–Alder adduct 3 with an approximately cis/trans = 1:1 mixture was obtained in the early stage of the reaction (Supporting Information File 1, Figure S3). Taken together, we can now propose a mechanism for the radical cation Diels–Alder

• ). Conditions: 1.0 M LiClO4/CH3NO2, carbon felt electrodes, 1.2 V vs Ag/AgCl, 0.7 F/mol. Oxidative SET-triggered reaction of aryl vinyl ether 1c. Conditions: 1.0 M LiClO4/CH3NO2, carbon felt electrodes, 1.2 V vs Ag/AgCl, 0.1 F/mol. Oxidative SET-triggered rearrangement of vinyl cyclobutane 4. Conditions: 1.0 M

Dialkyl dicyanofumarates and dicyanomaleates as versatile building blocks for synthetic organic chemistry and mechanistic studies

• Grzegorz Mlostoń and
• Heinz Heimgartner

Beilstein J. Org. Chem. 2017, 13, 2235–2251, doi:10.3762/bjoc.13.221

• reactions with diazomethane albeit in very low yields [29]. [2 + 2]-Cycloadditions The electron-deficient dicyanofumarates E-1 react with electron-rich ethenes, yielding cyclobutane derivatives as product of [2 + 2]-cycloadditions. Depending on the reaction conditions and on the type of the electron-rich

• ethene, the reaction occurs stereoselectively or with loss of the stereochemical arrangement of substituents. For example, 4-methoxystyrene (20) reacts with E-1b in 2,5-dimethyltetrahydrofuran in the presence of ZnCl2 with complete stereoselectivity and the cyclobutane derivative 21 is formed as the sole

• product [30] (Scheme 6). The analogous reaction with phenyl vinyl sulfide (22) gave the expected cyclobutane 23 exclusively. However, in the absence of ZnCl2, a mixture of 23 and 3,4-dihydro-2H-pyran 24 was obtained, with the latter compound formed through a competitive hetero-Diels–Alder reaction [30

Bridgehead vicinal diallylation of norbornene derivatives and extension to propellane derivatives via ring-closing metathesis

• Sambasivarao Kotha and
• Rama Gunta

Beilstein J. Org. Chem. 2016, 12, 1877–1883, doi:10.3762/bjoc.12.177

• as strained as cyclopropane or cyclobutane (norbornene, 100 kJ/mol; cyclopropane, 115 kJ/mol; cyclobutane, 110 kJ/mol) [4][5]. Some of the annulated norbornene derivatives undergo retro Diels–Alder (rDA) reactions at ambient temperature in the presence of methylaluminium dichloride and a reactive

The synthesis of functionalized bridged polycycles via C–H bond insertion

• Jiun-Le Shih,
• Po-An Chen and
• Jeremy A. May

Beilstein J. Org. Chem. 2016, 12, 985–999, doi:10.3762/bjoc.12.97

• its reactive equivalent, and then C–H insertion into a cyclopentyl methylene. Insertion into a methylene adjacent to the spirocyclic center in 69 would create a highly strained spirocyclic cyclobutane ring having an sp2 carbon center. Thus, the bicyclo[2.2.1]heptane 70 is the major product, but a

Natural products from microbes associated with insects

• Christine Beemelmanns,
• Huijuan Guo,
• Maja Rischer and
• Michael Poulsen

Beilstein J. Org. Chem. 2016, 12, 314–327, doi:10.3762/bjoc.12.34

• extract led to the isolation of a new tricyclic macrolactam named tripartilactam (24) [103]. Tripartilactam (24) contains an unprecedented cyclobutane moiety, which links the 8- and 18-membered rings, and it is most likely derived from a photochemically [2 + 2] cycloaddition reaction of the corresponding

Synthesis of Xenia diterpenoids and related metabolites isolated from marine organisms

• Tatjana Huber,
• Lara Weisheit and
• Thomas Magauer

Beilstein J. Org. Chem. 2015, 11, 2521–2539, doi:10.3762/bjoc.11.273

• [7.2.0]undecane ring system 31 as found in xeniaphyllanes [3]. Finally, double C–H oxidation furnishes the β-hydroxy aldehyde 32 which can undergo a retro-aldol reaction with concomitant opening of the cyclobutane ring to form dialdehyde 33 as the common biogenetic precursor of xenicins, xeniolides and

• . The ester group was selectively reduced and desilylation afforded alcohol 84. The generated primary alcohol was tosylated and regioselective deprotonation followed by intramolecular α-alkylation stereoselectively formed the cyclobutane ring. A final Wittig methylenation introduced the exocyclic double

Copper-catalyzed aerobic radical C–C bond cleavage of N–H ketimines

• Ya Lin Tnay,
• Gim Yean Ang and
• Shunsuke Chiba

Beilstein J. Org. Chem. 2015, 11, 1933–1943, doi:10.3762/bjoc.11.209

• having a strained cyclobutane ring did not form the desired oxaspirocyclohexadienone (Scheme 6). Instead, γ-bromoketone 8e was isolated in 44% yield along with nitrile 5a in 80% yield. The formation of γ-bromoketone 8e is most likely caused by radical ring opening from the transient cyclobutoxy radical I

A comprehensive study of olefin metathesis catalyzed by Ru-based catalysts

• Albert Poater and
• Luigi Cavallo

Beilstein J. Org. Chem. 2015, 11, 1767–1780, doi:10.3762/bjoc.11.192

• , Piers and co-workers demonstrated the bottom-bound geometry for a Ru-cyclobutane model compound by NMR data [46]. However, Grubbs and co-workers supported the side-bound pathway [47]. And this sort of discrepancy is displayed in Scheme 3, where the same catalyst shows two conformations, a and b, bottom

• coworkers [33]. Structurally, the Ru–C(metallacycle) bonds in 1, 2, 3 and 7 are rather similar, around 1.97–1.98 Å, see Figure 5a, while in 5 they are remarkably longer with 2.01 Å, probably due to the steric pressure of the t-Bu N-substituents. In all the cases the C–C bonds of the Ru–cyclobutane are

Star-shaped tetrathiafulvalene oligomers towards the construction of conducting supramolecular assembly

• Masahiko Iyoda and
• Masashi Hasegawa

Beilstein J. Org. Chem. 2015, 11, 1596–1613, doi:10.3762/bjoc.11.175

• were synthesized by Ortí, Martín, and co-workers (Figure 3) [44]. The pioneering studies on the synthesis of tetrakis(1,3-dithiol-2-ylidene)cyclobutane (8) and related [5] and [6]radialenes 9 and 10a,b were reported by Yoshida and co-workers in the 1980’s (Figure 4). These π-expanded TTFs 8–10a,b

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

• to generate cyclobutane derivative 262. Finally, the ring opening occurs with catalytic amounts of potassium hexacyanoferrate(III) in the presence of KF to deliver the fluorinated ferrocenophane 263 (Scheme 42). Okada and Nishimura [6] have reported the synthesis of syn-[2.n]metacyclophane 270 as a

Design and synthesis of novel bis-annulated caged polycycles via ring-closing metathesis: pushpakenediol

• Sambasivarao Kotha and
• Mirtunjay Kumar Dipak

Beilstein J. Org. Chem. 2014, 10, 2664–2670, doi:10.3762/bjoc.10.280

• ] cycloaddition strategies, which involve the DA reaction of 2,5-dialkyl-1,4-benzoquinone 10 and 1,3-cyclopentadiene (9) followed by the formation of the cyclobutane ring through a [2 + 2] photocycloaddition reaction (Figure 2). Later on, one can introduce two allyl groups by using traditional carbonyl chemistry

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

• heteroatom variants of the DVCPR, namely the vinylcyclopropane carbaldehyde–dihydrooxepine rearrangement [217], the vinylcyclopropane carbimine–dihydroazepine [217] rearrangement and the corresponding cyclobutane analogues [229][230][231]. A very stunning application [231] has been achieved using the Claisen

Less reactive dipoles of diazodicarbonyl compounds in reaction with cycloaliphatic thioketones – First evidence for the 1,3-oxathiole–thiocarbonyl ylide interconversion

• Valerij A. Nikolaev,
• Alexey V. Ivanov,
• Ludmila L. Rodina and
• Grzegorz Mlostoń

Beilstein J. Org. Chem. 2013, 9, 2751–2761, doi:10.3762/bjoc.9.309

• postulated structures. Owing to their diastereotopic nature, the four Me groups attached to the cyclobutane ring in 1,3-oxathioles 3a–g, derived from thioketone 1a, appeared in the 1H and 13C NMR spectra as two signals (each for 2 Me). This observation can be considered as an additional argument confirming

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

• catalyst provides a gold–allyl cationic species of type IX, which is the species undergoing the cycloaddition process with the diene [73]. Simple alkenes do also react with gold-activated allenamides to provide cyclobutane products, formally resulting from a [2 + 2] cycloaddition. Thus, independent

• of this intermediate and therefore facilitates the overall process. Finally, a ring-closing process through attack of the vinylgold species to the stabilized carbocation yields the cyclobutane system and regenerates the catalyst. In view of this mechanistic proposal, Mascareñas and López recently

Microflow photochemistry: UVC-induced [2 + 2]-photoadditions to furanone in a microcapillary reactor

• Sylvestre Bachollet,
• Kimitada Terao,
• Shin Aida,
• Yasuhiro Nishiyama,
• Kiyomi Kakiuchi and
• Michael Oelgemöller

Beilstein J. Org. Chem. 2013, 9, 2015–2021, doi:10.3762/bjoc.9.237

• photoreactor equipped with low wattage UVC-lamps. Conversion rates and isolated yields were compared to analogue batch reactions in a quartz test tube. In all cases examined, the microcapillary reactor furnished faster conversions and improved product qualities. Keywords: cycloaddition; cyclobutane; flow

• . The cyclobutane methine protons emerged as clearly separated signals between 2.35 and 2.90 ppm. Their 3J coupling constants were determined to be 2.9/3.6 and 6.7/7.5 Hz, thus confirming the cis-anti-cis geometry of 3. Under continuous flow conditions, conversion rates increased more rapidly despite

• 90 min and 99% after 8 h of irradiation (Table 2, entries 1 and 2), respectively. From the latter experiment, cyclobutane 5 was isolated in a low yield of just 30%. In CDCl3, the CH3-groups in 5 gave four singlets between 1.02–1.21 ppm. Likewise, the CH2O-bridge appeared at 4.25 and 4.40 ppm with a

Topochemical control of the photodimerization of aromatic compounds by γ-cyclodextrin thioethers in aqueous solution

• Hai Ming Wang and
• Gerhard Wenz

Beilstein J. Org. Chem. 2013, 9, 1858–1866, doi:10.3762/bjoc.9.217

• ]). Instead, packing of the two ANT molecules within the complex seems to determine the quantum yield Φ. Stereoselective photodimerization of acenaphthylene The photodimerization of ACE generally leads to mixtures of two isomeric cyclobutane derivatives, namely the syn and the anti dimers, as shown in Scheme

• %, were unprecedentedly high, significantly higher than that of free ACE in organic solvents such as toluene (5%), ethanol (4%), and methanol/water (20% v/v, 3%) [28]. The 1H NMR signals of cyclobutane (for the syn photodimer, δH = 4.84 ppm; for the anti photodimer, δH = 4.10 ppm) were monitored to

• exerted by γ-CD thioethers 1–7 in aqueous solution. The composition of the mixture of isomeric photodimers was determined from the intensities of the 1H NMR signals of the cyclobutane protons, which were assigned according to previous work [40]. The results including the respective syn/anti ratios are

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

• 10.3762/bjoc.9.106 Abstract Background: Localized singlet diradicals are in general quite short-lived intermediates in processes involving homolytic bond-cleavage and formation reactions. In the past decade, long-lived singlet diradicals have been reported in cyclic systems such as cyclobutane-1,3-diyls

• and formation reactions (Figure 1) [1][2]. The singlet diradicals are, in general, quite short-lived species due to the very fast radical–radical coupling reaction [3]. However, in the past decade, the singlet diradicals have been observed or even isolated in cyclic systems such as cyclobutane-1,3

A computational study of base-catalyzed reactions of cyclic 1,2-diones: cyclobutane-1,2-dione

• Nargis Sultana and
• Walter M. F. Fabian

Beilstein J. Org. Chem. 2013, 9, 594–601, doi:10.3762/bjoc.9.64

• Nargis Sultana Walter M. F. Fabian Department of Chemistry, University of Sargodha, Sargodha, Pakistan Institut für Chemie, Karl Franzens Universität Graz, Heinrichstr. 28, A-8010 Graz, Austria 10.3762/bjoc.9.64 Abstract The reaction of cyclobutane-1,2-dione with hydroxide was studied by a

• ] leads to ring contraction, e.g., the rearrangement of cyclobutane-1,2-dione (1) to 1-hydroxycyclopropanecarboxylate (2) [5][6][7]. In contrast, cyclobut-3-ene-1,2-diones 3 react to 2-oxobut-3-enoates 4 (at least formally according to path B) [8], whereas benzocyclobutene-1,2-diones 5 lead to 2

• best of our knowledge no attempt has been made so far to consider the additional pathways B and C in these reactions. Here we present a detailed computational study (DFT and ab initio) of the base-catalyzed reactions of cyclobutane-1,2-dione (1) taking into account all three possible pathways. Results

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

• illustration is provided by the central transformation in the total synthesis of (–)-dendrobine (4), where the carbamyl radical cyclisation is followed by rupture of the cyclobutane ring [8][9]. This operation, displayed in Scheme 1, starts with benzoate 1 and results in the formation of the carbon–nitrogen

• represents a model study for the total synthesis of gilvocarcin M (47), a natural C-glycoside [27]; while the latter illustrates the possibility of constructing a cyclobutane-containing tricyclic motif related to the one found in penitrem D, 50 [28]. The two-step formation of tetralone 53, starting from

• Scheme 15 by the synthesis of bicyclic cyclobutane derivatives 74 and 75 starting from 2-xanthyl cyclobutanone 73 [35]. Thus, depending on the distance between the terminal alkene and the phosphonate, a six- or a seven-membered ring may be fused onto the cyclobutane nucleus. This combination represents

Caryolene-forming carbocation rearrangements

• Quynh Nhu N. Nguyen and
• Dean J. Tantillo

Beilstein J. Org. Chem. 2013, 9, 323–331, doi:10.3762/bjoc.9.37

• side of the ring as the first-formed cyclobutane, converged to the structure of C shown in Figure 3 [41]. Locating a pathway for the conversion of C to D (Scheme 1) also proved difficult. We expected proton transfer from the C15 methyl group to C6 of the C6=C7 π-bond to result in tertiary carbocation D

The chemistry of bisallenes

• Henning Hopf and
• Georgios Markopoulos

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

Alkoxide-induced ring opening of bicyclic 2-vinylcyclobutanones: A convenient synthesis of 2-vinyl-substituted 3-cycloalkene-1-carboxylic acid esters

• Xiufang Ji,
• Zhiming Li,
• Quanrui Wang and
• Andreas Goeke

Beilstein J. Org. Chem. 2012, 8, 650–657, doi:10.3762/bjoc.8.72

• or acid derivatives makes this transformation a good supplementary method for the well-established Johnson–Claisen rearrangement. Keywords: alkoxide; cyclobutanones; esters; fused ring systems; ring opening; Introduction A great variety of methods are available for the synthesis of cyclobutane

• addition, the high electrophilicity of the carbonyl carbon atom, and the puckering of the cyclobutane caused by the substitution at C-2 and C-4, also offer both interesting preparative and mechanistic aspects [11]. The ease of ring opening of cyclobutanones is influenced by the strain of the four-membered

Recent advances in the gold-catalyzed additions to C–C multiple bonds

• He Huang,
• Yu Zhou and
• Hong Liu

Beilstein J. Org. Chem. 2011, 7, 897–936, doi:10.3762/bjoc.7.103

• bridging C–C bond and a formal [1,2]-alkynyl shift. Li et al. reported the first gold-catalyzed reaction of propargylcyclopropene systems 212 which affords benzene derivatives 213 in high yields [94] (Scheme 39). Only few efficient methods have emerged for the synthesis of cyclobutane derivatives, which

Intraannular photoreactions in pseudo-geminally substituted [2.2]paracyclophanes

• Henning Hopf,
• Vitaly Raev and
• Peter G. Jones

Beilstein J. Org. Chem. 2011, 7, 658–667, doi:10.3762/bjoc.7.78

• ), photodimerization to the corresponding cyclobutane derivative occurs readily, and the photoproduct can be saponified to the corresponding pseudo-geminal diamine and truxinic acid (6) in excellent yield, thus allowing its stereospecific synthesis. We believe that the use of the [2.2]paracyclophane scaffold as a

• shown [22] by time-resolved photoelectron spectroscopy (TR-PES) that the pseudo-geminal divinyl derivative 7 can only react from its anti,anti-conformation (anti referring to the orientation of the vinyl substituent to the neighboring ethano bridge) to yield the cyclobutane derivative 8. The syn,anti

• any detectable photoproducts. The success in preparing cyclobutane derivative 4 (n = 1) from the corresponding cinnamophane diester 3 (n = 1, quantitative yield) led us to attempt to prepare the corresponding cyclobutane dialdehyde derivative 16 (Scheme 6). Unfortunately, although this was the only