Asymmetric synthesis of a stereopentade fragment toward latrunculins

• Benjamin Joyeux,
• Antoine Gamet,
• Nicolas Casaretto and
• Bastien Nay

Beilstein J. Org. Chem. 2023, 19, 428–433, doi:10.3762/bjoc.19.32

• a 1,5-anti induction of the aldol reaction [18][19][20] based on chiral alkoxy partner 9. Furthermore, it could be envisaged to reduce the resulting β-hydroxyketone 7 in a diastereoselective manner to obtain a 1,3-diol. This synthetic strategy could thus bring new stereochemical opportunities to

Total synthesis of ent-pavettamine

• Memory Zimuwandeyi,
• Manuel A. Fernandes,
• Amanda L. Rousseau and
• Moira L. Bode

Beilstein J. Org. Chem. 2021, 17, 1440–1446, doi:10.3762/bjoc.17.99

• 17, followed by acetonide protection of the 1,3-diol functionality to yield the previously synthesized intermediate 4. The acetonide protecting group was chosen because of its stability under the future reaction conditions in addition to it being a convenient monitor of the relative configuration of

• the 1,3-diol motif [19]. The group is also associated with ease of deprotection, which is well documented in carbohydrate and sugar chemistry [20]. Comparison of our new route involving trityl and TBS protections with our previously published acetonide protection route for the synthesis of 4, showed

• , whose values differ for the syn-1,3 diol when compared to the anti-1,3-diol as described after an extensive study by Rychnovsky et al. [21]. The reductive amination of the aldehyde with benzylamine allowed for the introduction of a protected terminal amine group to the C5 fragment, yielding 19 in a

Stereoselective synthesis and transformation of pinane-based 2-amino-1,3-diols

• Ákos Bajtel,
• Mounir Raji,
• Matti Haukka,
• Ferenc Fülöp and
• Zsolt Szakonyi

Beilstein J. Org. Chem. 2021, 17, 983–990, doi:10.3762/bjoc.17.80

• -2-one; stereoselective; tautomerism; Introduction The best known 2-amino-1,3-diol derivative sphingosine (1) plays a crucial role in intracellular signaling as second messenger, and its derivatives called sphingolipids are also critical for cell growth, cell differentiation, cell recognition, and

• the lack of a readily available natural sources and the high biological importance of sphingolipid analogues, their synthesis has been the subject of numerous studies [16]. The key step for the synthesis is the stereoselective construction of the 2-amino-1,3-diol moiety of the molecules. Generally

• -1,3-diol [21][22]. For instance, deoxoprosophylline (5) as a cyclic 2-amino-1,3-diol target molecule was prepared by Kokatla et al. in an 8 step synthesis starting from Perlin aldehydes, via Pd(OH)2-catalyzed reductive azidoketon cyclisation [23]. Another synthetic pathway involves a stereoselective

Total synthesis of decarboxyaltenusin

• Lucas Warmuth,
• Aaron Weiß,
• Marco Reinhardt,
• Anna Meschkov,
• Ute Schepers and
• Joachim Podlech

Beilstein J. Org. Chem. 2021, 17, 224–228, doi:10.3762/bjoc.17.22

• Lewis acid, while the utilization of 1.5 equivalents led to a significant overreaction with the predominant formation of 5-bromobenzene-1,3-diol (59%) together with a smaller amount of the required product 8 (30%). The subsequent protection with the TBS group yielded the known aryl bromide 9a [24] with

Recent synthesis of thietanes

• Jiaxi Xu

Beilstein J. Org. Chem. 2020, 16, 1357–1410, doi:10.3762/bjoc.16.116

• 1966 [32]. They treated 3,5-dichloropentan-2-ol (9) with K2S to produce 1-(thietan-2-yl)ethan-1-ol (10) in 65% yield (Scheme 1). In 2007, Nishizono and co-workers used 2,2-bis(bromomethyl)propane-1,3-diol (11) as starting material to prepare thietanose nucleosides 2 and 14. They first carried out a

• as inhibitor of kinases, insecticides, and acaricides, its sulfur analogue, 6-amino-2-thiaspiro[3,3]heptane (28) was prepared from the cheap starting material 2,2-bis(bromomethyl)propane-1,3-diol (11). Compound 11 was converted into 3-(tert-butoxycarbonyl)-1,1-bis(hydroxymethyl)aminocyclobutane (25

Fluorinated phenylalanines: synthesis and pharmaceutical applications

• Laila F. Awad and
• Mohammed Salah Ayoup

Beilstein J. Org. Chem. 2020, 16, 1022–1050, doi:10.3762/bjoc.16.91

• of type III 2.1. Fluorination of protected (1R,2R)-2-amino-ʟ-phenylpropane-1,3-diol Recently, Okuda et al. reported the synthesis of (3R)-3-fluoro-ʟ-phenylalanine (121) from (1R,2R)-2-amino-ʟ-phenylpropane-1,3-diol (116). Thus, Boc-protection of the amine group in 116 followed by the protection of

• -difluorophenylalanine 115. Synthesis of β-fluorophenylalanine via 2-amino-1,3-diol derivatives. Synthesis of β-fluorophenylalanine derivatives via the oxazolidinone chiral auxiliary 122. Synthesis of β-fluorophenylalanine from pyruvate hemiketal 130. Synthesis of β-fluorophenylalanine (136) via fluorination of β

Towards the total synthesis of chondrochloren A: synthesis of the (Z)-enamide fragment

• Jan Geldsetzer and
• Markus Kalesse

Beilstein J. Org. Chem. 2020, 16, 670–673, doi:10.3762/bjoc.16.64

• ). A subsequent transesterification under mild conditions with Bu2SnO provided dihydroxy ester 7 in 72% yield. The 1,3-diol in 7 was methylated with an excess of the Meerwein reagent and TIPDS-removal afforded ester 9 in good yields. A double TBS-protection and liberation of the primary alcohol

Application of chiral 2-isoxazoline for the synthesis of syn-1,3-diol analogs

• Juanjuan Feng,
• Tianyu Li,
• Jiaxin Zhang and
• Peng Jiao

Beilstein J. Org. Chem. 2019, 15, 1840–1847, doi:10.3762/bjoc.15.179

• product in 95% yield, which was converted into tert-butyl (3S,5R)-6-hydroxy-3,5-O-isopropylidene-3,5-dihydroxyhexanoate in 14 steps through a β-hydroxy ketone. Keywords: β-hydroxy ketone; cycloaddition; 1,3-diol; isoxazoline; silyl nitronate; Introduction The chiral 1,3-diol structure is widespread in a

• broad spectrum of natural products [1][2]. (3R)-β-Hydroxy-δ-lactone or its open-ring equivalent (3R)-syn-3,5-dihydroxypentanoic acid, is a common structure in naturally occurring mevastatin (or compactin), lovastatin or closely related statins, and synthetic statins. Either the syn or anti-1,3-diol

• chiral β-hydroxy-δ-lactone moiety or its equivalents, pioneered by Wong [42], is equally competitive. Here, we report the preparations of tert-butyl (3S,5R)-6-hydroxy-3,5-O-isopropylidene-3,5-dihydroxyhexanoate and related syn-1,3-diol analogs from a chiral 2-isoxazoline (Scheme 1b). This work is part of

N-(1-Phenylethyl)aziridine-2-carboxylate esters in the synthesis of biologically relevant compounds

• Iwona E. Głowacka,
• Aleksandra Trocha,
• Andrzej E. Wróblewski and
• Dorota G. Piotrowska

Beilstein J. Org. Chem. 2019, 15, 1722–1757, doi:10.3762/bjoc.15.168

• diversified compounds. In this review we wish to focus attention on applications of 5–8 in syntheses of biologically important compounds having a 2-amino-1,3-disubstituted propane unit implanted into their structures because vicinal amino alcohol and 2-aminopropane-1,3-diol scaffolds are present in many

Olefin metathesis catalysts embedded in β-barrel proteins: creating artificial metalloproteins for olefin metathesis

• Daniel F. Sauer,
• Johannes Schiffels,
• Takashi Hayashi,
• Ulrich Schwaneberg and
• Jun Okuda

Beilstein J. Org. Chem. 2018, 14, 2861–2871, doi:10.3762/bjoc.14.265

• nm indicated the presence of the GH-type catalyst. Finally, the peak for the biohybrid conjugate was observed in ESI–TOF–MS suggesting successful covalent anchoring. Beside ring-closing metathesis (RCM) of 2,2-diallylpropane-1,3-diol to yield the corresponding cyclopentane derivative, the synthesized

Microfluidic light-driven synthesis of tetracyclic molecular architectures

• Javier Mateos,
• Nicholas Meneghini,
• Marcella Bonchio,
• Nadia Marino,
• Tommaso Carofiglio,
• Xavier Companyó and
• Luca Dell’Amico

Beilstein J. Org. Chem. 2018, 14, 2418–2424, doi:10.3762/bjoc.14.219

• manipulation involved the treatment of 4a with PhMgBr, converting the lactone moiety into the corresponding aromatic ketone. Product 8a formed in 71% yield without diastereoisomeric loss. Finally, LiAlH4 reduction of 4a furnished the bicyclic 1,3-diol 9a in quantitative yield, again without the need of

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

• hindrance, starburst effect [18][58][59], against authentic free rotation upon heating. This fact was not quite surprising because we previously reported a related situation in the case of some G-0 dendrons as N,N’-disubstituted 2-chloro-4,6-diamino-s-triazines with bulky azaspirodecane and propane-1,3-diol

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

• family known to date. A structure was proposed by the Small group based on mass fragmentation and 1H/2D NMR spectroscopic data. This structure, which features a tetraenoate (lower) side chain with a terminal 1,3-diol motif was once again confirmed by total synthesis in the Kishi laboratory; the relative

• and absolute stereochemistry of the compound was assigned by NMR in conjunction with HPLC on a chiral stationary phase [59]. Of note, the stereochemistry of the 1,3-diol motif of the polyunsaturated side chain of mycolactone F (8) is antipodal to the same motif in all other natural mycolactones with

• known configuration. Intriguingly, salt water fish-infesting M. marinum produces a remote diastereomer [60] of mycolactone F (dia-mycolactone F, 9) that exhibits the regular configuration of the 1,3-diol motif at the end of the lower side chain [61]. Most recently, the Kishi laboratory isolated two new

Biosynthetic origin of butyrolactol A, an antifungal polyketide produced by a marine-derived Streptomyces

• Enjuro Harunari,
• Hisayuki Komaki and
• Yasuhiro Igarashi

Beilstein J. Org. Chem. 2017, 13, 441–450, doi:10.3762/bjoc.13.47

• intriguing feature of this molecule is the highly oxygenated carbon chain in which eight hydroxy groups, one of which is used for lactone formation, are contiguously aligned. A 1,3-diol is a common structural element in aliphatic polyketides because the incorporation of malonate-precursors gives rise to the

Catalytic asymmetric formal synthesis of beraprost

• Yusuke Kobayashi,
• Ryuta Kuramoto and
• Yoshiji Takemoto

Beilstein J. Org. Chem. 2015, 11, 2654–2660, doi:10.3762/bjoc.11.285

• benzylic bromination followed by elongation of the C3 unit [22]. To this end, the ester group at the C1 position of 15 was reduced by lithium borohydride, and the resultant 1,3-diol protected to give acetal 16 [16]. After various experiments, selective bromination of the methyl group on the aromatic ring

Recent advances in copper-catalyzed asymmetric coupling reactions

• Fengtao Zhou and
• Qian Cai

Beilstein J. Org. Chem. 2015, 11, 2600–2615, doi:10.3762/bjoc.11.280

• stereogenic centers, derived from tartaric acid, giving the product as a single isomer in good yield (Scheme 11). Sugimura et al. [31] expanded this method by introducing chiral 1,3-diol-derived tethers into the substrates, delivering the corresponding coupling products in excellent diastereoselectivity

• -permethyl-tellimagrandin I. Total synthesis of (+)-gossypol. Total synthesis of (−)-mastigophorene A. Total synthesis of isokotanin. Synthesis of dimethyl[7]thiaheterohelicenes. Intramolecular coupling with chiral ortho-substituents. Chiral 1,3-diol-derived tethers in the diastereoselective synthesis of

Synthesis of bi- and bis-1,2,3-triazoles by copper-catalyzed Huisgen cycloaddition: A family of valuable products by click chemistry

• Zhan-Jiang Zheng,
• Ding Wang,
• Zheng Xu and
• Li-Wen Xu

Beilstein J. Org. Chem. 2015, 11, 2557–2576, doi:10.3762/bjoc.11.276

• highest activity. In 2010, Nandurdikar et al. linked the two (or four) molecules of NO donor prodrugs together through the triazole spacers [22], which has potential application as NO-releasing materials. They first prepared the benzylidene-protected 2,2-di(azidomethyl)propane-1,3-diol containing the

Terminal lipophilization of a unique DNA dodecamer by various nucleolipid headgroups: Their incorporation into artificial lipid bilayers and hydrodynamic properties

• Emma Werz and
• Helmut Rosemeyer

Beilstein J. Org. Chem. 2015, 11, 913–929, doi:10.3762/bjoc.11.103

• -phosphoethanolamine (POPE) and 1-palmitoyl-2-oleyl-sn-glycero-3-phosphocholine (POPC) were purchased from Avanti Polar Lipids (Alabaster, Al), n-decane from Alfa Aesar (D-Karlsruhe), potassium chloride (KCl), 3-morpholinopropane-1-sulfonic acid (MOPS) and 2-amino-2-(hydroxymethyl)propane-1,3-diol (TRIS) were

Mechanical stability of bivalent transition metal complexes analyzed by single-molecule force spectroscopy

• Manuel Gensler,
• Christian Eidamshaus,
• Maurice Taszarek,
• Hans-Ulrich Reissig and
• Jürgen P. Rabe

Beilstein J. Org. Chem. 2015, 11, 817–827, doi:10.3762/bjoc.11.91

• of 2-(hydroxymethyl)-2-methylpropane-1,3-diol (313 mg, 2.33 mmol) in dry DMF (25 mL) was added NaOH (600 mg, 15.0 mmol). After 15 min stirring at room temperature, 4-fluoropyridine (777 mg, 8.00 mmol) was added. The mixture was heated to reflux for 4 days and after cooling to room temperature diluted

Diastereoselective and enantioselective conjugate addition reactions utilizing α,β-unsaturated amides and lactams

• Katherine M. Byrd

Beilstein J. Org. Chem. 2015, 11, 530–562, doi:10.3762/bjoc.11.60

• reactions proceeded in good yields (71–84%) and high diastereoselectivities. This work has been useful because the syn-1,3-diol moiety is commonly observed in many natural products, most notably in polyol macrolide antibiotics [72][73][74]. Performing CA reactions on chiral lactams has been a common method

Bis(vinylenedithio)tetrathiafulvalene analogues of BEDT-TTF

• Erdal Ertas,
• İlknur Demirtas and
• Turan Ozturk

Beilstein J. Org. Chem. 2015, 11, 403–415, doi:10.3762/bjoc.11.46

• were synthesized to provide the possibility of intramolecular hydrogen bonding through the hydroxy groups [57]. The half ET analogue 61 was obtained from the reactions of either the dianion 5 or the zinc-complex 59 with 2-bis(bromomethyl)propane-1,3-diol (60, Scheme 10). As the hydroxy groups could

Specific DNA duplex formation at an artificial lipid bilayer: fluorescence microscopy after Sybr Green I staining

• Emma Werz and
• Helmut Rosemeyer

Beilstein J. Org. Chem. 2014, 10, 2307–2321, doi:10.3762/bjoc.10.240

• -hydroxymethylpropane-1,3-diol (TRIS) were purchased from Roth (Karlsruhe, Germany). All oligonucleotides 4–10 (Figure 1) were synthesized, purified and characterized by MALDI–TOF mass spectrometry by Eurogentec SA (Liege, Belgium). In each case the detected mass confirmed the corresponding calculated mass. MALDI–TOF

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

• conjugate addition of methanol and lactonization. The second cyclic building block, syn-dihydropyran 188, could be synthesized by a highly diastereoselective 6-endo-trig cyclization of an allylic 1,3-diol, which was developed by Hanessian and co-workers [141]. The required allylic 1,3-diol would also be

Synthesis and solvodynamic diameter measurements of closely related mannodendrimers for the study of multivalent carbohydrate–protein interactions

• Yoann M. Chabre,
• Alex Papadopoulos,
• Alexandre A. Arnold and
• René Roy

Beilstein J. Org. Chem. 2014, 10, 1524–1535, doi:10.3762/bjoc.10.157

• the benzene carbon, hence differing by a distance of only ~1.5 Å. Schemes 2–4 illustrate the syntheses of 9-mers 12 and 21 using the same trimesic acid core, together with a phloroglucinol template to initiate the synthesis of homologue 17, but incorporating 2-amino-2-hydroxymethylpropane-1,3-diol as

Synthesis of the spiroketal core of integramycin

• Evgeny. V. Prusov

Beilstein J. Org. Chem. 2013, 9, 2446–2450, doi:10.3762/bjoc.9.282

• PMB-protected 3-hydroxypropanal via Horner–Wadsworth-Emmons olefination, reduction to the allylic alcohol and Sharples epoxidation [8] (Scheme 2). Subsequent Cu-catalyzed epoxide-opening using methylmagnesium bromide [9] produced an inseparable mixture of 1,2- and 1,3-diol products, which upon