The reaction of arylmethyl isocyanides and arylmethylamines with xanthate esters: a facile and unexpected synthesis of carbamothioates

• Narasimhamurthy Rajeev,
• Toreshettahally R. Swaroop,
• Ahmad I. Alrawashdeh,
• Shofiur Rahman,
• Abdullah Alodhayb,
• Seegehalli M. Anil,
• Kuppalli R. Kiran,
• Chandra,
• Paris E. Georghiou,
• Kanchugarakoppal S. Rangappa and
• Maralinganadoddi P. Sadashiva

Beilstein J. Org. Chem. 2020, 16, 159–167, doi:10.3762/bjoc.16.18

• reported the synthesis of thiazoles from xanthate esters [31]. In continuation of this ongoing work, we planned to synthesize 5-alkoxy-4-arylthiazoles 3 by the sodium hydride/DMF-mediated reaction of arylmethyl isocyanides 2 with S-alkyl xanthate esters 1 or O-aryl/O-alkyl dithiocarbonates. Unexpectedly

Synthesis, liquid crystalline behaviour and structure–property relationships of 1,3-bis(5-substituted-1,3,4-oxadiazol-2-yl)benzenes

• Afef Mabrouki,
• Malek Fouzai,
• Armand Soldera,
• Abdelkader Kriaa and
• Ahmed Hedhli

Beilstein J. Org. Chem. 2020, 16, 149–158, doi:10.3762/bjoc.16.17

• et al. investigated on the liquid crystalline behaviour of some bis(phenyl-1,3,4-oxadiazolyl)benzene derivatives with varied number and length of terminal alkoxy chains [32]. The authors established that the mesogenicity is strongly enhanced in materials with four long terminal alkoxy substituents

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

• excellent yields, with the hydroperoxide functional group acting as a precursor of an alkoxy radical to control site-selective carbon-centered radical formation. Allylic fluorination: In 2011, the group of Nguyen [92] developed the nucleophilic fluorination of allylic trichloroacetimidates, as shown in

Nanopatterns of arylene–alkynylene squares on graphite: self-sorting and intercalation

• Tristan J. Keller,
• Joshua Bahr,
• Kristin Gratzfeld,
• Nina Schönfelder,
• Marcin A. Majewski,
• Marcin Stępień,
• Sigurd Höger and
• Stefan-S. Jester

Beilstein J. Org. Chem. 2019, 15, 1848–1855, doi:10.3762/bjoc.15.180

• graphite and 1,2,4-trichlorobenzene. Self-sorting leads to the intermolecular interdigitation of alkoxy side chains of identical length. Voids inside and between the squares are occupied by intercalated solvent molecules, which numbers depend on the sizes and shapes of the nanopores. In addition, planar

• with different numbers of sides [18], that are scalable to some extent [19]. The long alkoxy side chains mediate sufficient compound solubility and compound adsorption on highly oriented pyrolytic graphite (HOPG) that acts as a template [20][21], and determine the intermolecular interaction [22][23][24

• ]. The patterns formed by the polygons, especially the bigons, triangles, squares, and hexagons as well as molecular spoked wheels, are alike if the dithiophene corner pieces are exchanged by other corners, or if the side length is altered [19]. However, in all these cases the alkyl/alkoxy side chains at

Recent advances on the transition-metal-catalyzed synthesis of imidazopyridines: an updated coverage

• Gagandeep Kour Reen,
• Ashok Kumar and
• Pratibha Sharma

Beilstein J. Org. Chem. 2019, 15, 1612–1704, doi:10.3762/bjoc.15.165

Synthesis, enantioseparation and photophysical properties of planar-chiral pillar[5]arene derivatives bearing fluorophore fragments

• Guojuan Li,
• Chunying Fan,
• Guo Cheng,
• Wanhua Wu and
• Cheng Yang

Beilstein J. Org. Chem. 2019, 15, 1601–1611, doi:10.3762/bjoc.15.164

• that differs from the common macrocycles is the planar chirality resulting from the different orientations of the alkoxy substituents on the rims. Theoretically, eight conformers can be formed including diastereomeric ones: (Sp,Sp,Sp,Sp,Sp), (Rp,Sp,Sp,Sp,Sp), (Rp,Rp,Sp,Sp,Sp), (Rp,Sp,Rp,Sp,Sp) and

• their antipodal enantiomers: (Rp,Rp,Rp,Rp,Rp), (Sp,Rp,Rp,Rp,Rp), (Sp,Sp,Rp,Rp,Rp), (Sp,Rp,Sp,Rp,Rp). Among them, the enantiomeric per-Sp (Sp,Sp,Sp,Sp,Sp) and per-Rp (Rp,Rp,Rp,Rp,Rp) conformers (abbreviated as Sp and Rp, respectively), in which all of the alkoxy substituents at both rims are oriented in

Synthesis of dipolar molecular rotors as linkers for metal-organic frameworks

• Sebastian Hamer,
• Fynn Röhricht,
• Marius Jakoby,
• Ian A. Howard,
• Xianghui Zhang,
• Christian Näther and
• Rainer Herges

Beilstein J. Org. Chem. 2019, 15, 1331–1338, doi:10.3762/bjoc.15.132

• groups are known to exhibit the highest electron-withdrawing effect among the uncharged small functional groups [54]. As electron-donating substitutents, amino groups exhibit the strongest effects, especially if tris-alkyl substituted. However, we chose alkoxy substituents for our design, because

• phenylenediamine (1,2-diaminobenzene) units are strongly coordinating ligands which interfere with MOF formation. Moreover, alkoxy substituents provide several advantages in synthesis. While methoxy substituents are known and common donors, calculations showed that bridged alkoxy substituents such as the

Photochemical generation of the 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) radical from caged nitroxides by near-infrared two-photon irradiation and its cytocidal effect on lung cancer cells

• Ayato Yamada,
• Manabu Abe,
• Yoshinobu Nishimura,
• Shoji Ishizaka,
• Masashi Namba,
• Taku Nakashima,
• Kiyofumi Shimoji and
• Noboru Hattori

Beilstein J. Org. Chem. 2019, 15, 863–873, doi:10.3762/bjoc.15.84

• at the para-position of the p-nitrophenyl group in 2a. As observed in the OP uncaging reaction at 365 nm, the efficiency of the TP-induced TEMPO uncaging reaction of 2a was almost three times higher than that of 2b in benzene. This is attributed to the substituent effect of the meta-alkoxy group on

Diastereo- and enantioselective preparation of cyclopropanol derivatives

• Marwan Simaan and
• Ilan Marek

Beilstein J. Org. Chem. 2019, 15, 752–760, doi:10.3762/bjoc.15.71

• Marwan Simaan Ilan Marek The Mallat Family Laboratory of Organic Chemistry, Schulich Faculty of Chemistry, Technion-Israel Institute of Technology, Haifa, 32000, Israel 10.3762/bjoc.15.71 Abstract The diastereoselective carbocupration reaction of alkoxy-functionalized cyclopropene derivatives

• group [90][91][92]. Conclusion In conclusion, we have successfully merged the regio- and diastereoselective carbocupration reaction of alkoxy-functionalized cyclopropenes with electrophilic oxidation of the resulting cyclopropylcopper species to afford 2,2,3,3-polysubstituted cyclopropanol derivatives

Tuning the stability of alkoxyisopropyl protection groups

• Zehong Liang,
• Henna Koivikko,
• Mikko Oivanen and
• Petri Heinonen

Beilstein J. Org. Chem. 2019, 15, 746–751, doi:10.3762/bjoc.15.70

• chromatography without degradation. The compatibility of these protecting groups in parallel use with benzoyl and silyl groups was verified. The stabilities of the different alkoxy acetal protecting groups were compared by following the kinetics of their hydrolysis at 25.0 °C in buffered solutions through an

• HPLC method. In the pH range 4.94 to 6.82 the hydrolysis reactions are of first order in the hydronium ion. The rate of hydrolysis correlates with the electron-donating or electron-withdrawing ability of the corresponding alkoxy group. The studied 2-alkoxypropan-2-yl groups and the relative rate

• [7]. We realized that the lability of the acetal group can be easily steered by varying the alkoxy group, while preserving other beneficial properties of the protecting groups. On the other hand, structural modifications can also affect the lipophilicity of the protected compounds. The present study

The LANCA three-component reaction to highly substituted β-ketoenamides – versatile intermediates for the synthesis of functionalized pyridine, pyrimidine, oxazole and quinoxaline derivatives

• Tilman Lechel,
• Roopender Kumar,
• Mrinal K. Bera,
• Reinhold Zimmer and
• Hans-Ulrich Reissig

Beilstein J. Org. Chem. 2019, 15, 655–678, doi:10.3762/bjoc.15.61

• reaction is very broad and almost all types of nitriles and carboxylic acids have successfully been used. The alkoxy group introduced via the allene component is also variable and hence the subsequent transformation of this substituent into a hydroxy group can be performed under different conditions

• -labile alkoxy substituents such as a 2-(trimethylsilyl)ethoxy group are required for the conversion of β-ketoenamides into 5-acetyl-substituted oxazoles OX, again compounds with high potential for subsequent functional group transformations. For acid labile β-ketoenamides bearing bulky substituents the

• carboxylic acids with tertiary centers are possible candidates for the route to β-ketoenamides. The last example shown in Scheme 5 demonstrates that allenes with chiral alkoxy substituents are also suitable starting materials in the three-component reaction. We did not study lithiated carbohydrate-derived

Synthesis and selected transformations of 2-unsubstituted 1-(adamantyloxy)imidazole 3-oxides: straightforward access to non-symmetric 1,3-dialkoxyimidazolium salts

• Grzegorz Mlostoń,
• Małgorzata Celeda,
• Katarzyna Urbaniak,
• Marcin Jasiński,
• Vladyslav Bakhonsky,
• Peter R. Schreiner and
• Heinz Heimgartner

Beilstein J. Org. Chem. 2019, 15, 497–505, doi:10.3762/bjoc.15.43

• importance of this procedure is reflected in the multistep reactions applied for the preparation of some bioactive imidazole derivatives [22][23]. However, the preparation of imidazole-2-thiones with N-alkoxy groups, starting with the corresponding 2-unsubstituted imidazole 3-oxides, has not yet been

• diverse 1-(adamantyloxy)imidazole 3-oxides as well as to 1,3-dialkoxyimidazolium salts, which are attractive substrates for syntheses of other imidazole derivatives, including a new group of 1-alkoxy and 1,3-dialkoxyimidazol-2-ylidenes. In all described cases, it is of interest to probe the influence of

• the alkoxy residues on the stability and reactivity of the hitherto unknown nucleophilic carbenes bearing this groups at N(1) and/or N(3) atoms. In addition, it is worth mentioning that 1,3-dibenzyl-4,5-dimethylimidazolium chloride as well as its 2-methyl-substituted analogue are well known imidazole

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

• Raines reported examples of RCM, CM and ROMP in heterogeneous conditions with hydrophobic catalysts [21][33]. Blechert prepared alkoxy- and cyano-substituted catalysts 19 and 20 from G-II (Scheme 5) [34], while Raines and co-workers employed the conventional catalysts G-II and HG-II [35]. Blechert and

Syntheses and chemical properties of β-nicotinamide riboside and its analogues and derivatives

• Mikhail V. Makarov and
• Marie E. Migaud

Beilstein J. Org. Chem. 2019, 15, 401–430, doi:10.3762/bjoc.15.36

• Dowex 50WX8 resin. According to the patent publication of Livingston et al. [60], the chloridate 32 may be reacted not only with water but also with alcohols, such as isopropanol, ethanol, propanol, methanol, butanol, to result in the mono-substitution of a chlorine atom in 32 with corresponding alkoxy

• group and – after quenching with water – to give NMN analogues with one alkoxy group at the phosphorus atom. The resulting compounds were purified by column chromatography on an aminopropyl-modified silica gel Quadrasil AP column to yield the pure NMN analogues in low to moderate yields (8–40%). The

Sigmatropic rearrangements of cyclopropenylcarbinol derivatives. Access to diversely substituted alkylidenecyclopropanes

• Guillaume Ernouf,
• Jean-Louis Brayer,
• Christophe Meyer and
• Janine Cossy

Beilstein J. Org. Chem. 2019, 15, 333–350, doi:10.3762/bjoc.15.29

• trimethylsilyldiazomethane, the resulting α-alkoxy methyl esters 58a–l, incorporating an alkylidenecyclopropane moiety, were obtained as single detectable diastereomers [61]. As in the previously discussed [3,3]-sigmatropic rearrangements, the observed stereochemical outcome was in agreement with a six-membered chair-like

• rearrangement was then triggered by addition of Me3SiCl (4 equiv) and KHMDS (4 equiv), (THF, −78 °C to rt). Subsequent hydrolysis and treatment with trimethylsilyldiazomethane afforded the corresponding α-alkoxy methyl esters 66a–h, and 66k–n possessing a 3,3-difluoroalkylidenecyclopropane scaffold. This two

• by Rh/C occurred on the less hindered face of the alkene and gave rise to cyclopropyl α-alkoxy ester 72 as a single detectable diastereomer. When Pd/C was used as the catalyst, cleavage of the PMB group took place concomitantly and the α-hydroxy ester 73 arising from addition of hydrogen on the less

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

• -rich aryl groups could deliver higher yields than that with electron-deficient ones. As outlined in Scheme 12, a tert-butoxy radical and a methyl radical were generated from cleavage of DTBP at the reaction temperature. Aldehyde 48 is easily transformed into acyl radical 50 in the presence of an alkoxy

• complex 126 is initially formed from the process of ligand exchange between the substrate and AgF2. The alkoxy radical 98 is produced via a single-electron oxidation by Ag–O bond homolysis. As a feature of the cyclopropane system, the radical 98 goes through a ring fission to form the alkyl radical 99

Silanediol versus chlorosilanol: hydrolyses and hydrogen-bonding catalyses with fenchole-based silanes

• Falco Fox,
• Jörg M. Neudörfl and
• Bernd Goldfuss

Beilstein J. Org. Chem. 2019, 15, 167–186, doi:10.3762/bjoc.15.17

• ]) to the corresponding silanediols. While hydrolyses of dichlorosilanes have been studied extensively [23][24][25], hydrolyses of alkoxy dichlorosilanes are much less explored. Hydrogen bond donor (HBD) catalysis is an emerging field in organic synthesis [26][27][28], employing, e.g., squaramides [29

• [47]. Compared to these stable carbon-connected silanediols, the readily accessible alkoxy silanediols undergo fast condensation reactions which often lead to unknown and insoluble polysiloxanes [50][51]. Previously, our group reports syntheses and applications of symmetric biphenyl-2,2`-bisfenchol (5

• ] is examined (Scheme 4). In close analogy to BIFOXSiCl2 (7), di-tert-butoxydichlorosilane is substituted with tertiary alkoxy groups. While the close analogy of BIFOXSiCl2 (7) and ((CH3)3CO)2SiCl2 would make a comparison of these two dichlorosilanes preferable, the instability of the latter against

Regioselective addition of Grignard reagents to N-acylpyrazinium salts: synthesis of substituted 1,2-dihydropyrazines and Δ⁵-2-oxopiperazines

• Valentine R. St. Hilaire,
• William E. Hopkins,
• Yenteeo S. Miller,
• Srinivasa R. Dandepally and
• Alfred L. Williams

Beilstein J. Org. Chem. 2019, 15, 72–78, doi:10.3762/bjoc.15.8

• recently showed that 3-alkoxy-substituted N-acylpyrazinium salts can be selectively reduced by tributyltin hydride to afford 1,2-dihydropyrazines in good to excellent yields [9]. There have been other reports involving the addition of TMS-ketene acetals to pyrazinium salts [10][11][12]. A double

• either an ethyl or benzyl group on the pyrazinium salts gave an 81% yield for both 10 and 11 (Figure 1). Reacting a Grignard with pyrazinium salts disubstituted with electron-donating alkoxy groups gave us the desired dihydropyrazine in moderate to good yields of 45–88% (Figure 1, compounds 8, 9a,b

Cobalt- and rhodium-catalyzed carboxylation using carbon dioxide as the C1 source

• Tetsuaki Fujihara and
• Yasushi Tsuji

Beilstein J. Org. Chem. 2018, 14, 2435–2460, doi:10.3762/bjoc.14.221

• scope was examined (Scheme 11). Allylbenzene was converted into its corresponding carboxylated product 12a in an isolated 68% yield, and various functionalized allylarenes bearing trifluoromethyl (11b) and alkoxy (11c,d) substituents were tolerated. The selectivity of the reaction was demonstrated with

Cationic cobalt-catalyzed [1,3]-rearrangement of N-alkoxycarbonyloxyanilines

• Itaru Nakamura,
• Mao Owada,
• Takeru Jo and
• Masahiro Terada

Beilstein J. Org. Chem. 2018, 14, 1972–1979, doi:10.3762/bjoc.14.172

• promoted the [1,3]-alkoxy rearrangement of N-alkoxyaniline [15], the cationic NHC-Cu catalyst generated from IPrCuBr and AgSbF6 was totally inefficient for the present reaction; 1a was decomposed under the reaction conditions (Table 1, entry 19). Whereas AgSbF6 promoted the reaction at 60 °C (Table 1

Design, synthesis and structure of novel G-2 melamine-based dendrimers incorporating 4-(n-octyloxy)aniline as a peripheral unit

• Cristina Morar,
• Pedro Lameiras,
• Attila Bende,
• Gabriel Katona,
• Emese Gál and
• Mircea Darabantu

Beilstein J. Org. Chem. 2018, 14, 1704–1722, doi:10.3762/bjoc.14.145

• (ethynyl)-s-triazine and various icosanyloxyphenylazides) with liquid crystalline and luminescent properties [22]. On the other hand, mesogenic supramolecular perylene bisimide assemblies with a number of 2-amino-4,6-bis[(4-alkoxy)phenylamino]-s-triazines [23], amphiphilic azobenzene-containing linear

• (in B) and rigid 1,4-phenylene with adjustable alkoxy-spacers (n = 1, 3, in C1 and C3, respectively). G-1 chloro- and piperazine-dendrons, D-Cl and D-N

  NH, as well as central building blocks B, C1 and C3, had s-triazine rings linked by C(s-triazine)–N(exocyclic) partial double bonds, which exist due

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

• (-CH2X), alkoxy (-CH2O), aryloxy (PhO), aryl (Ph) and alkyl (-CH2) substituents on the epoxide. The virtues of this protocol are the low cost and ready availability of NBS, its moisture and air stability as well as low toxicity. The reaction is characterized by short reaction time, good to high product

• alkene to form radical 87. This intermediate undergoes oxidation followed by decomposition to provide the alkoxy radical intermediate 88, which then affords the β-hydroxy sulfide 81 upon protonation. The considerably stronger S–S bonds of the dialkyl disulfides and the lower stability of the expected

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

• , similar deformylation by action of hypervalent iodine has also been demonstrated: the β-fragmentation reaction of an anomeric alkoxy radical of carbohydrates was mediated by a hypervalent iodine reagent [73]. The reaction results in the formation of carbohydrates with a reduction of one carbon. From the

• viewpoint of the synthetic method, the reaction would be useful for dehomologation of aldoses and preparation of chiral synthons deriving from sugars. The reaction procedure involves the initial formation of an alkoxy anomeric radical by a hypervalent iodine reagent in the presence of iodine, which triggers

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

Phosphodiester models for cleavage of nucleic acids

• Satu Mikkola,
• Tuomas Lönnberg and
• Harri Lönnberg

Beilstein J. Org. Chem. 2018, 14, 803–837, doi:10.3762/bjoc.14.68