Systematic synthetic study of four diastereomerically distinct limonene-1,2-diols and their corresponding cyclic carbonates

• Hiroshi Morikawa,
• Jun-ichi Yamaguchi,
• Shun-ichi Sugimura,
• Masato Minamoto,
• Yuuta Gorou,
• Hisatoyo Morinaga and
• Suguru Motokucho

Beilstein J. Org. Chem. 2019, 15, 130–136, doi:10.3762/bjoc.15.13

• oxide) and conditions, the desired diastereomers were synthesised in moderate to high yields with, in most cases, high stereoselectivity. Comparison of the NMR data of the obtained diols and carbonates revealed that the four different diastereomers of each compound could be distinguished by reference to

• significance, largely because LM derivatives with their versatile functionality can be effectively utilised in organic and polymer chemistry. (4R)-Limonene-1,2-diols (LMdiols) are some of the most important LM derivatives because they act as precursors of bioactive molecules [12][13][14]. Furthermore, LMdiol

• was initially applied in this study to 1a (Scheme 2) as an analogy to the reaction of 1d. The reaction proceeded smoothly giving the corresponding LMdiol 2a in an excellent yield (Scheme 3). It is also possible to synthesise 5CCs from diols by reaction with triphosgene (Scheme 2). It is well known

Copolymerization of epoxides with cyclic anhydrides catalyzed by dinuclear cobalt complexes

• Yo Hiranoi and
• Koji Nakano

Beilstein J. Org. Chem. 2018, 14, 2779–2788, doi:10.3762/bjoc.14.255

• (or diacid derivatives) with diols. The ready availability of structurally diverse diacids and diols provides access to a wide range of polyesters. In this method, an extremely high conversion of the carboxy and hydroxy groups should be achieved for synthesizing high molecular weight polyesters

Unprecedented nucleophile-promoted 1,7-S or Se shift reactions under Pummerer reaction conditions of 4-alkenyl-3-sulfinylmethylpyrroles

• Takashi Go,
• Akane Morimatsu,
• Hiroaki Wasada,
• Genzoh Tanabe,
• Osamu Muraoka,
• Yoshiharu Sawada and
• Mitsuhiro Yoshimatsu

Beilstein J. Org. Chem. 2018, 14, 2722–2729, doi:10.3762/bjoc.14.250

• (diols). Seleno-Pummerer reactions of 3-selanylmethylpyrroles also proceeded via in situ generation of selenoxides, followed by a treatment with TBAH. Keywords: hydroamination; Pummerer reaction; pyrrole; pyrroloazepine; 1,7-sulfur shift; Introduction Pyrrolo- and indoloazepine skeletons are chemical

• N-methallylselenopyrrole 6b also gave the pyrroloazepine 10b, which was formed via the 1,7-Se shift reaction. While N-3-methylbut-2-enyl derivatives 4c and 6c yielded 1,7-S- and Se-shifted diols 9c and 10c, respectively. Interestingly, the reaction of N-cinnamylpyrroles 4d and 6d exclusively

• afforded trans-azepines 11d and 12d via intramolecular cyclization. The same procedure applied to the bulky N-(3-methylbut-2-enyl) derivatives 4e and 6e yielded the corresponding diols 9e and 10e. Whether the Pummerer reactions yielded cyclised products or not was strongly affected by the substituent

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

• substrate 117, which was subjected to RCM with the aid of G-II catalyst 2 to produce a mixture of products 119 and 121 in combined 47% yield. It should be noted that the resulting product 121 was obtained through isomerization of the terminal double bond followed by RCM. Later, oxidation of diols 119 and

Synthesis of eunicellane-type bicycles embedding a 1,3-cyclohexadiene moiety

• Alex Frichert,
• Peter G. Jones and
• Thomas Lindel

Beilstein J. Org. Chem. 2018, 14, 2461–2467, doi:10.3762/bjoc.14.222

• conversion to the diastereomer by oxidation and reduction. Conformational analysis of some of the resulting diols obtained under McMurry conditions was complicated by the presence of several conformers of similar energy. The pinacol coupling appears to start at the ketone, as indicated by the selective

• two conformers in CDCl3. Thus, it was to be explored how open-ring cyclohexadiene precursors would be synthesized and behave under McMurry conditions, and how stable the resulting [8.4.0]bicycles would be. Normally, McMurry conditions lead to the formation of alkenes, but medium-sized ring 1,2-diols

• -containing 8 adopts two distinct major conformations in CDCl3, whereas diastereomeric diols 18 and 19 prefer only one, which were elucidated by NOESY spectroscopy. In upcoming studies we will address the synthesis of systems that contain a cyclohexene ring keeping the sp2–sp2 bridge of the product from the

Investigation of the electrophilic reactivity of the biologically active marine sesquiterpenoid onchidal and model compounds

• Melissa M. Cadelis and
• Brent R. Copp

Beilstein J. Org. Chem. 2018, 14, 2229–2235, doi:10.3762/bjoc.14.197

• Z diester 21 (10%, Scheme 3). The reduction of diesters 20 (E) and 21 (Z) with LiAlH4 afforded diols 22 and 23 in 63% and 67% yield, respectively. Subsequent oxidation of 22 with DMP afforded dialdehyde 11 in 31% yield. Correspondingly, the reaction of diol 23 with DMP afforded a mixture of

• and 26 with LiAlH4 afforded the corresponding diols 27 and 28 in 61% and 71% yield, respectively, which upon oxidation (DMP) afforded dialdehydes 15 and 16 in 49% and 73% yield, respectively. The reaction of dialdehyde 15 with Ac2O and pyridine afforded enol acetate 17 in 43% yield after purification

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

• cyclohexene diester 94 (1:1 mixture of diastereomers) [64]. Reduction and subsequent separation by silica gel column chromatography gave diols 95a and 95b, the hydroxy groups of which were protected to give di-TBDPS derivatives 96a and 96b. The resulting cyclohexenylsilanes 96a and 96b were subjected to the

Electrochemical Corey–Winter reaction. Reduction of thiocarbonates in aqueous methanol media and application to the synthesis of a naturally occurring α-pyrone

• Ernesto Emmanuel López-López,
• José Alvano Pérez-Bautista,
• Fernando Sartillo-Piscil and
• Bernardo A. Frontana-Uribe

Beilstein J. Org. Chem. 2018, 14, 547–552, doi:10.3762/bjoc.14.41

• ; thiocarbonates; Findings The Corey–Winter reaction (also known as the Corey–Winter reductive olefination) is a chemical transformation that permits the conversion of 1,2-diols A into E-alkenes C via the formation and reduction of a cyclic thiocarbonate intermediate B (Scheme 1) [1][2]. In general this reaction

• convert thiocarbonates derived from 1,2-diols containing the 6-pentyl-2H-pyran-2-one framework to trans-alkenes by means of electrochemical reduction in an H-type separated cell was developed. The thiocarbonate functional group can be reduced using a vitreous carbon electrode in MeOH/H2O 80:20 with AcOH

Gram-scale preparation of negative-type liquid crystals with a CF₂CF₂-carbocycle unit via an improved short-step synthetic protocol

• Tatsuya Kumon,
• Shohei Hashishita,
• Takumi Kida,
• Shigeyuki Yamada,
• Takashi Ishihara and
• Tsutomu Konno

Beilstein J. Org. Chem. 2018, 14, 148–154, doi:10.3762/bjoc.14.10

• to the LC display industry. The stereochemistry in the ring-closing metathesis step 5→4 was determined as follows. As depicted in Table 2, it has been generally recognized that the melting points of trans-1,4-disubstituted cyclohexane-1,4-diols are much higher than those of the corresponding cis

Fluorination of some highly functionalized cycloalkanes: chemoselectivity and substrate dependence

• Attila Márió Remete,
• Melinda Nonn,
• Santos Fustero,
• Matti Haukka,
• Ferenc Fülöp and
• Loránd Kiss

Beilstein J. Org. Chem. 2017, 13, 2364–2371, doi:10.3762/bjoc.13.233

• behavior in fluorination in view of selectivity and to explore substrate dependency and chemodifferentiation. Based on the different stereochemical structures of the selected model diols as well as the nature of the N-protecting group used, we expected differences in their chemical behavior under

Synthesis of ergostane-type brassinosteroids with modifications in ring A

• Vladimir N. Zhabinskii,
• Darya A. Osiyuk,
• Yuri V. Ermolovich,
• Natalia M. Chaschina,
• Tatsiana S. Dalidovich,
• Miroslav Strnad and
• Vladimir A. Khripach

Beilstein J. Org. Chem. 2017, 13, 2326–2331, doi:10.3762/bjoc.13.229

• ,3α-, and 2β,3β-dihydroxy-, 3-keto-, 3α- and 3β-hydroxy-, 2α-hydroxy-3-keto-) were synthesized from 2α,3α-diols in a few simple steps (Corey–Winter reaction, epoxidation, oxidation, hydride reduction, etc.). Keywords: biosynthetic precursors; brassinosteroids; diols; epibrassinolide; epicastasterone

• -keto-22,23-diols was synthesized and assessed for biological activities in non-plant models. Some of the studied compounds showed a marked cytotoxicity against human cancer cell lines MCF-7 and LNCaP [11][12][13]. We tested two approaches for the transformation of epicastasterone (1) and

• the contrary, no correlation was observed between the corresponding protons in compound 22, which is consistent with the α-orientation of the epoxide ring. 2β,3β-, 2β,3α- and 2α,3β-diols of type 6–8 Experiments on the identification of steroidal phytohormones in immature seeds of Phaseolus vulgaris

Remarkable functions of sn-3 hydroxy and phosphocholine groups in 1,2-diacyl-sn-glycerolipids to induce clockwise (+)-helicity around the 1,2-diacyl moiety: Evidence from conformation analysis by ¹H NMR spectroscopy

• Yoshihiro Nishida,
• Mengfei Yuan,
• Kazuo Fukuda,
• Kaito Fujisawa,
• Hirofumi Dohi and
• Hirotaka Uzawa

Beilstein J. Org. Chem. 2017, 13, 1999–2009, doi:10.3762/bjoc.13.196

• Equation 2 [18]. From the vicinal coupling constants (3J Hz) of H1proR and H1proS signals, the fractional populations (%) of the three staggered conformers are calculated. Equation 1 is a standard equation, in which the three staggered conformers have the dihedral angles of ± 60° or 180° around 1,2-diols

Selective enzymatic esterification of lignin model compounds in the ball mill

• Ulla Weißbach,
• Saumya Dabral,
• Laure Konnert,
• Carsten Bolm and
• José G. Hernández

Beilstein J. Org. Chem. 2017, 13, 1788–1795, doi:10.3762/bjoc.13.173

• matched/mismatched interactions of the diastereomeric diols and the chiral biocatalyst. Similarly, the unsubstituted model compound 1e reacted smoothly to give 3e in 92% yield. Purification of 3e was done by filtration through a pad of celite, since it proved unstable towards standard purification

The chemistry and biology of mycolactones

• Matthias Gehringer and
• Karl-Heinz Altmann

Beilstein J. Org. Chem. 2017, 13, 1596–1660, doi:10.3762/bjoc.13.159

Strategies toward protecting group-free glycosylation through selective activation of the anomeric center

• A. Michael Downey and
• Michal Hocek

Beilstein J. Org. Chem. 2017, 13, 1239–1279, doi:10.3762/bjoc.13.123

Synthesis of ribavirin 2’-Me-C-nucleoside analogues

• Fanny Cosson,
• Aline Faroux,
• Jean-Pierre Baltaze,
• Jonathan Farjon,
• Régis Guillot,
• Jacques Uziel and
• Nadège Lubin-Germain

Beilstein J. Org. Chem. 2017, 13, 755–761, doi:10.3762/bjoc.13.74

• with tetrabutylammonium fluoride leading to the mixture of diols 17 and 18 in quantitative yield which were easily separated (Scheme 3). Finally, the aminolysis of compound 17 followed by catalytic hydrogenolysis in the presence of palladium chloride led to the desired compound 3 [22] (Scheme 4

Exploring endoperoxides as a new entry for the synthesis of branched azasugars

• Svenja Domeyer,
• Mark Bjerregaard,
• Henrik Johansson and
• Daniel Sejer Pedersen

Beilstein J. Org. Chem. 2017, 13, 644–647, doi:10.3762/bjoc.13.63

• set for the central dihydroxylation reaction that would give access to key intermediates 20 and 21 (Scheme 4). To our delight dihydroxylation with potassium osmate in the presence of citric acid was smooth and gave excellent yields of diols 20 and 21 [11]. Diols 20 and 21 were found to be unstable

Studies directed toward the exploitation of vicinal diols in the synthesis of (+)-nebivolol intermediates

• Runjun Devi and
• Sajal Kumar Das

Beilstein J. Org. Chem. 2017, 13, 571–578, doi:10.3762/bjoc.13.56

• heterocycles has been tremendous, its synthetic utility toward chiral benzo-annulated heterocycles is relatively limited. Thus, in the search for wider applications of Sharpless asymmetric dihydroxylation-derived diols for the synthesis of benzo-annulated heterocycles, we report herein our studies in the

• , method 3) whereupon the overall yield of the reaction sequence diminished [11]. On the other hand, the Sharpless asymmetric dihydroxylation (SAD) has been a workhorse as a synthetic tool for accessing enantiopure vicinal diols [21]. The extensive work in this field has resulted in the discovery of a

• superior in terms of operational simplicity as SAE, it can be run at 0 °C in water as a co-solvent and under an atmosphere open to air. The application of SAD-derived vicinal diols in the synthesis of acyclic molecules and saturated heterocycles has been astonishing. However, their utilities in the

Orthogonal protection of saccharide polyols through solvent-free one-pot sequences based on regioselective silylations

• Serena Traboni,
• Emiliano Bedini and
• Alfonso Iadonisi

Beilstein J. Org. Chem. 2016, 12, 2748–2756, doi:10.3762/bjoc.12.271

• saccharide alcohols [34], the first catalytic tin-mediated procedure for regioselective benzylation/allylation of hydroxy groups incorporated into vicinal diols [35], and three alternative acetalation protocols [36]. Besides the avoided use of solvents, these approaches appear advantageous owing to their

A versatile route to polythiophenes with functional pendant groups using alkyne chemistry

• Xiao Huang,
• Li Yang,
• Rikard Emanuelsson,
• Jonas Bergquist,
• Maria Strømme,
• Martin Sjödin and
• Adolf Gogoll

Beilstein J. Org. Chem. 2016, 12, 2682–2688, doi:10.3762/bjoc.12.265

• light yellow oil by chromatography with a yield of 64%. The yield of the transetherification product was influenced by two factors. Substrate concentrations below 0.5 M resulted in much less polymerization, leaving more diols for transetherification. However, still lower concentrations of less than 0.1

• % could be obtained, but this would not be sufficient for large scale production, besides considering the environmental impact of requiring a halogenated solvent. Comparing the structural difference between diols 2 and 7, these results emphasized that the isolation of the alkyne from the ethylenediol by

Formose reaction controlled by boronic acid compounds

• Toru Imai,
• Tomohiro Michitaka and
• Akihito Hashidzume

Beilstein J. Org. Chem. 2016, 12, 2668–2672, doi:10.3762/bjoc.12.263

• optimizing the conditions of the formose reaction [6][7][8][9][10][11][12][13][14][15]. However, the selective formose reaction is still an important subject of investigation [16]. It is known that boronic acid compounds form esters with diols, e.g., sugars [17][18]. Boronic acid compounds may thus stabilize

Synthesis of polyhydroxylated decalins via two consecutive one-pot reactions: 1,4-addition/aldol reaction followed by RCM/syn-dihydroxylation

• Michał Malik and
• Sławomir Jarosz

Beilstein J. Org. Chem. 2016, 12, 2602–2608, doi:10.3762/bjoc.12.255

• ]. After desilylation followed by protection of the free hydroxy with a benzoyl group and deprotection of the isopropylidene moiety, diols 20 and 24 were obtained. With α,β-unsaturated ketones 17 and 18 and two enantiomeric, optically pure aldehydes (R)- and (S)-10 in hand, we started to study the 1,4

• the subsequent syn-dihydroxylation with NaIO4 as a stoichiometric oxidant in the presence of catalytic amounts of CeCl3 (15 mol %). As a result, in the case of diolefin 25 as substrate, a separable mixture of diols (dr = 8:1; 27 being the major isomer) was obtained in fair yield (56%). The same

Isosorbide and dimethyl carbonate: a green match

• Fabio Aricò and
• Pietro Tundo

Beilstein J. Org. Chem. 2016, 12, 2256–2266, doi:10.3762/bjoc.12.218

• isosorbide was almost quantitative (95.2%). Similarly poly(aliphaticdiol-co-isosorbide carbonate)s were prepared via melt polycondensation of DMC with isosorbide and several aliphatic diols employing Li(acac) and the TiO2/SiO2-based catalyst (Scheme 4) [85]. High-molecular-weight (Mw = 32,600) and optically

The direct oxidative diene cyclization and related reactions in natural product synthesis

• Juliane Adrian,
• Leona J. Gross and
• Christian B. W. Stark

Beilstein J. Org. Chem. 2016, 12, 2104–2123, doi:10.3762/bjoc.12.200

• prepared from commercially available neryl acetate (15). The auxiliary-controlled, permanganate-promoted oxidation of diene 16 proceeded selectively at low temperatures, affording the corresponding diastereomeric THF diols as an inseparable mixture (dr 7:1, major stereoisomer shown in Scheme 6). Compound

• [84]. Thus, the corresponding THF diols were obtained in 55% yield. In addition to the desired THF diol 28a for the total synthesis of cis-solamin A (29), small amounts of its diastereoisomer 28b were isolated (dr 10:1, Scheme 8 left). Similar permanganate-mediated oxidative cyclizations were also

• [92][97]. In this case, two permanganate-promoted type A oxidative cyclization reactions were used to establish the two THF rings of this acetogenin (Scheme 11). Both THF diols 43 and 47 were isolated as pure diastereoisomers with high diastereocontrol (dr 9:1 for 43 and dr 8.7:1 for 47, respectively

Ionic liquids as transesterification catalysts: applications for the synthesis of linear and cyclic organic carbonates

• Maurizio Selva,
• Alvise Perosa,
• Sandro Guidi and
• Lisa Cattelan

Beilstein J. Org. Chem. 2016, 12, 1911–1924, doi:10.3762/bjoc.12.181

• should therefore implement greener reactions, such as the direct carboxylation of diols by CO2, for which however, effective catalysts are currently not available. The Asahi Kasei process also highlights that the synthesis of DMC by transesterification of ethylene carbonate with methanol does not

• synthesize organic carbonates consists in the acid or base-catalyzed transesterification of dimethyl carbonate (DMC), the simplest organic carbonate, with alcohols R–OH or diols to yield either acyclic organic carbonates or cyclic carbonates, respectively (Scheme 8). A literature survey on the synthesis of

• diols can be carried out in the presence of basic (e.g., tertiary phosphines and amines, alkali metal hydroxides, alkoxides, halides, carbonates, alkali metal exchanged faujasites and hydrotalcites) or acidic catalysts or co-catalysts, and under thermal (non-catalytic) conditions. All applicable