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

• the (+)-microcosamine A the protected piperidine (2S,3R,6S)-197 served as a starting material and was first converted into the N-Boc derivative while selective desilylation exposed the hydroxymethyl group to give (2S,3R,6S)-199. Oxidation to the respective aldehyde was accomplished with Dess–Martin

• periodinane and olefination was carried out as already described. Acidic hydrolysis of N-Boc and O-TBDMS groups afforded (2S,3R,6S)-194b which was identical with the natural (+)-microcosamine A. 1-Deoxynojirimycin was discovered in several natural species and later found as a potent inhibitor of glycosidases

Synthesis and biological evaluation of truncated derivatives of abyssomicin C as antibacterial agents

• Leticia Monjas,
• Peter Fodran,
• Johanna Kollback,
• Carlo Cassani,
• Thomas Olsson,
• Maja Genheden,
• D. G. Joakim Larsson and
• Carl-Johan Wallentin

Beilstein J. Org. Chem. 2019, 15, 1468–1474, doi:10.3762/bjoc.15.147

• targeted compounds 1 and 2 in 17% and 30% yield over the two steps, respectively. For the final step, several oxidation agents were evaluated, and the highest yields were achieved with Dess–Martin periodinane, which converted 22 and 23 to 1 and 2 in 24% and 41% yield, respectively. Biological evaluation

• equiv), THF, rt, 16 h, 73% (22: R = Me) and 74% (23: R = CH2CH2Ph). d) Dess–Martin periodinane (2.5 equiv), CH2Cl2, rt, 2 h, 24% (1: R = Me) and 41% (2: R = CH2CH2Ph). Minimum inhibitory concentrations (MIC) of compounds 1, 2, 4 and 5 against S. aureus and two strains of MRSA. Supporting Information

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

• -Acetoxymethyl-substituted pyrimidine derivatives offer many options for the introduction of new substituents. For example the removal of the acetyl group by treatment with potassium carbonate in methanol and oxidation with Dess–Martin periodinane (DMP) converted PM61 and PM63 into aldehydes PM69 and PM71 in

• PM61 and PM63, oxidations to formyl-substituted pyrimidines PM69 and PM71 and synthesis of nitrile PM72 (DMP = Dess–Martin periodinane). Synthesis of pyrimidinyl-substituted alkyne PM74 and conversion into furopyrimidine PM75 and Sonogashira reaction of PO3 with ethynylbenzene to pyrimidine N-oxide

The mechanochemical synthesis of quinazolin-4(3H)-ones by controlling the reactivity of IBX

• Md Toufique Alam,
• Saikat Maiti and
• Prasenjit Mal

Beilstein J. Org. Chem. 2018, 14, 2396–2403, doi:10.3762/bjoc.14.216

• benzaldehydes, aniline and IBX under ball-milling conditions an explosion was observed (Figure 1a; Caution! see experimental section) [30][31] and similar observations were made with Dess–Martin periodinane (DMP). On the other hand, benzamide was found to be unreactive with IBX and no reaction was observed

Preparation and X-ray structure of 2-iodoxybenzenesulfonic acid (IBS) – a powerful hypervalent iodine(V) oxidant

• Irina A. Mironova,
• Pavel S. Postnikov,
• Rosa Y. Yusubova,
• Akira Yoshimura,
• Thomas Wirth,
• Viktor V. Zhdankin,
• Victor N. Nemykin and
• Mekhman S. Yusubov

Beilstein J. Org. Chem. 2018, 14, 1854–1858, doi:10.3762/bjoc.14.159

• product of its acetylation Dess–Martin periodinane (DMP) are the most common oxidants used for selective oxidation of alcohols to carbonyl compounds as well as for a variety of other synthetically useful oxidative transformations [10][11]. IBX and DMP are mild oxidants with a relatively low reactivity

Hypervalent organoiodine compounds: from reagents to valuable building blocks in synthesis

• Gwendal Grelier,
• Benjamin Darses and
• Philippe Dauban

Beilstein J. Org. Chem. 2018, 14, 1508–1528, doi:10.3762/bjoc.14.128

• ]. Review Tandem additions λ5-Iodanes such as the Dess–Martin periodinane or IBX [26], and λ3-iodanes such as benziodoxolones [27], are versatile reagents in organic synthesis. These are often used, respectively, for the oxidation of alcohols or carbonyl compounds, and in atom-transfer reactions. These

• stereoselective trans iodo-benzoylation of glycals using a combination of IBX and molecular iodine, that is considered as a source of I+ formed from the in situ generated hypoiodite species [30]. The controlled oxidation of various N-(alkyl)- and N-(aryl)pyrroles with Dess–Martin periodinane also leads to

Rapid transformation of sulfinate salts into sulfonates promoted by a hypervalent iodine(III) reagent

• Elsa Deruer,
• Vincent Hamel,
• Samuel Blais and
• Sylvain Canesi

Beilstein J. Org. Chem. 2018, 14, 1203–1207, doi:10.3762/bjoc.14.101

• ). To verify our hypothesis tosyl-sulfinate 1 was treated with iodanes such as sodium periodate (NaIO4), Dess-Martin periodinane (DMP) [33], 2-iodoxybenzoic acid (IBX) [34], (diacetoxyiodo)benzene (DIB), phenyliodine(III) bis(trifluoroacetate) (PIFA) in the presence of methanol. (III)-Iodanes and (V

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

• repeated the synthesis of 12 through a molecular bromination–dehydrobromination sequence starting with 162 [137]. Hypervalent iodine(V)-based reagents such as IBX (or 2-iodoxybenzoic acid) and Dess–Martin periodinane (DMP) are commonly used in organic synthesis as oxidizing agent to form both unsaturated

• alcohol 285. Oxidation with Dess–Martin periodinane of the alcohol 285 followed by ring-closing metatheses in the presence of 1 mol % of the second generation Grubbs catalyst (287) gave the 5H-benzo[7]annulene-5,6(7H)-dione monoketal 288 in nearly quantitative yield. The hydrolysis of 288 with excess p

Selective carboxylation of reactive benzylic C–H bonds by a hypervalent iodine(III)/inorganic bromide oxidation system

• Toshifumi Dohi,
• Shohei Ueda,
• Kosuke Iwasaki,
• Yusuke Tsunoda,
• Koji Morimoto and
• Yasuyuki Kita

Beilstein J. Org. Chem. 2018, 14, 1087–1094, doi:10.3762/bjoc.14.94

• determined to be the best in terms of product yield. No reaction was observed in the absence of sodium bromide (Table 1, entry 9) and other representative hypervalent iodine(III) reagents, such as PIFA and PhI(OH)OTs, and pentavalent Dess–Martin periodinane and IBX, were inferior for this carboxylation when

Hypervalent iodine-mediated Ritter-type amidation of terminal alkenes: The synthesis of isoxazoline and pyrazoline cores

• Sang Won Park,
• Soong-Hyun Kim,
• Jaeyoung Song,
• Ga Young Park,
• Darong Kim,
• Tae-Gyu Nam and
• Ki Bum Hong

Beilstein J. Org. Chem. 2018, 14, 1028–1033, doi:10.3762/bjoc.14.89

• -iodoxybenzoic acid) and DMP (Dess–Martin periodinane) (Table 1, entries 7 and 8) gave similar yields to the background reaction. Lastly, a Lewis acid screen (Table 1, entries 9–12) was performed. Among the tested Lewis acids, AlCl3, SnCl4, TiCl4, TMSOTf and BF3·Et2O, the latter was found to be the best choice

2-Iodo-N-isopropyl-5-methoxybenzamide as a highly reactive and environmentally benign catalyst for alcohol oxidation

• Takayuki Yakura,
• Tomoya Fujiwara,
• Akihiro Yamada and
• Hisanori Nambu

Beilstein J. Org. Chem. 2018, 14, 971–978, doi:10.3762/bjoc.14.82

• oxidants have been widely employed for oxidation in organic synthesis [1][2][3][4][5][6][7][8][9] because they are nonmetallic, less toxic, and easy to handle, and they allow mild reaction conditions in most cases. Pentavalent iodine reagents such as Dess–Martin periodinane (DMP, 1) [10] and 2

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

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

• ketone with Dess–Martin periodinane afforded 12a in 87% yield whereas the reaction of the less reactive isomer 11b led to 12b in 44% yield. With the aim to get some explanations for the different reactivities observed for the two isomers 10a and 10b, we investigated the structure of the less reactive

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

• –Doering oxidation conditions [15]. However, when the same conditions were applied to alcohol 4 it resulted in a complex mixture. Other oxidation procedures, including TPAP [16], Dess–Martin periodinane [17] and TEMPO [18] were attempted but in all instances complex mixtures were obtained and none of the

Stereo- and regioselectivity of the hetero-Diels–Alder reaction of nitroso derivatives with conjugated dienes

• Lucie Brulíková,
• Aidan Harrison,
• Marvin J. Miller and
• Jan Hlaváč

Beilstein J. Org. Chem. 2016, 12, 1949–1980, doi:10.3762/bjoc.12.184

• the corresponding hydroxamic acids using, for example, periodate [14], Dess–Martin periodinane [64], Swern oxidation conditions [65], lead and silver oxide [66], and transition-metal oxidation with peroxide as the oxidant [67]. In a recent work by Tusun dirhodium caprolactamate [68], and the aerobic

Selective bromochlorination of a homoallylic alcohol for the total synthesis of (−)-anverene

• Frederick J. Seidl and
• Noah Z. Burns

Beilstein J. Org. Chem. 2016, 12, 1361–1365, doi:10.3762/bjoc.12.129

• avoided exposure to strong bases or reducing agents, a limitation that significantly guided the choice of reagents and conditions for the subsequent steps. Dess–Martin periodinane oxidation of alcohol 6 followed by Horner–Wadsworth–Emmons olefination with triethyl 2-phosphonopropionate (9) furnished the

• equiv), acetone, 65 °C, 3 h; c) Dess–Martin periodinane (1.2 equiv), NaHCO3 (5 equiv), CH2Cl2, 0 °C to rt; d) triethyl 2-phosphonopropionate 9 (1.5 equiv), n-BuLi (1.2 equiv), 1:1 THF/acetonitrile, 0 °C, 5 min; e) DIBAL−H (3 equiv), CH2Cl2, −78 °C, 20 min; f) NBS (1.2 equiv), ClTi(OiPr)3 (1.1 equiv), 20

• mol % Ti(OiPr)4, 10 mol % (S,R)-4, 0.025 M hexanes, −15 °C, 42 h; g) Dess–Martin periodinane (1.2 equiv), NaHCO3 (5 equiv), CH2Cl2, 0 °C to rt; h) CBr4 (2 equiv), PPh3 (4 equiv), CH2Cl2, 0 °C, 10 min; i) Et3N (5 equiv), dimethyl phosphonate (4 equiv), DMF, rt, 5 min. Optimization of a selective

A cross-metathesis approach to novel pantothenamide derivatives

• Jinming Guan,
• Matthew Hachey,
• Lekha Puri,
• Vanessa Howieson,
• Kevin J. Saliba and
• Karine Auclair

Beilstein J. Org. Chem. 2016, 12, 963–968, doi:10.3762/bjoc.12.95

• molecule to be extended to pantothenamide 16. As outlined in Scheme 3, 16 was assembled from 11d by first oxidation to the corresponding aldehyde 12 using Dess–Martin periodinane in wet DCM. Further oxidation to the carboxylic acid 13 was achieved using mild chlorite oxidation. The product was used in the

Stereoselective synthesis of hernandulcin, peroxylippidulcine A, lippidulcines A, B and C and taste evaluation

• Marco G. Rigamonti and
• Francesco G. Gatti

Beilstein J. Org. Chem. 2015, 11, 2117–2124, doi:10.3762/bjoc.11.228

• to −30 °C). Treatment of 7 with Dess–Martin periodinane (DMP) [23] in CH2Cl2 at room temperature gave ketone 8 ([α]D +11.0° (c 1.0, CHCl3)) in 90% yield. The most difficult step of this synthetic route is the dehydrogenation of ketone 8. Since our main interest is focused on the taste evaluation of

Total synthesis of panicein A₂

• Lili Yeung,
• Lisa I. Pilkington,
• Melissa M. Cadelis,
• Brent R. Copp and
• David Barker

Beilstein J. Org. Chem. 2015, 11, 1991–1996, doi:10.3762/bjoc.11.215

• minutes, giving 14 in an excellent 94% yield. Hydrogenolysis of the alkene in 14 using Pd/C in MeOH proceeded in 2 hours, providing alcohol 15 which was then oxidised to the desired ketone 13 with Dess–Martin periodinane in 75% yield over two steps. Although this approach was ultimately two steps longer

Towards inhibitors of glycosyltransferases: A novel approach to the synthesis of 3-acetamido-3-deoxy-D-psicofuranose derivatives

• Maroš Bella,
• Miroslav Koóš and
• Chun-Hung Lin

Beilstein J. Org. Chem. 2015, 11, 1547–1552, doi:10.3762/bjoc.11.170

• ). Subsequently, the selective protection of the primary hydroxy group in diol 5 as trityl ether under standard conditions followed by the oxidation of the free secondary hydroxy group in 3-acetamido-3-deoxy-4,5-O-isopropylidene-6-O-pivaloyl-1-O-trityl-D-altritol (6) with Dess–Martin periodinane yielded a

Articulated rods – a novel class of molecular rods based on oligospiroketals (OSK)

• Pablo Wessig,
• Roswitha Merkel and
• Peter Müller

Beilstein J. Org. Chem. 2015, 11, 74–84, doi:10.3762/bjoc.11.11

• /PPh3. vii: Cu/C, Et3N. viii: K2CO3/MeOH. ix: CBr4/PPh3/NaN3). Macrocyclization of articulated rod 25. Synthesis of building blocks 27–29 (i: 1. pyrene-1-ylacetic acid, DCC/DMAP, 68%; 2. Dess–Martin periodinane 89%. ii: 1. cinnamoyl chloride, iPr2NEt, 94%; 2. Dess–Martin periodinane, 86%. iii: K2CO3

• –Martin-periodinane. iii: pentaerythritol, pTsOH (cat.). iv: 2-(4-methoxybenzyloxy)acetic acid, DCC, HOBt. v: (COCl)2/DMSO. vi: NaH, TMSCl, TMSOTf, vii DDQ, DCM, buffer pH 7). Synthesis of articulated rod 11 (i: CBr4, PPh3, NaN3. ii: K2CO3/MeOH. iii: Cu/C DCM/MeOH 1:1, cat. Et3N). Sequential deprotection

• ); 0.013 % (w/v) (line 3) and 0.02 % (w/v) (line 4) at 37 °C. Comparison of photochemical reactivity of 32b, 33a, 39 (left). Irradiation UV spectrum of 32b in ACN (right, t = 0, 0.5, 1, 1.5, 2.5, 4, 8, 16 min). Synthesis of building block 8 (i: trimethylsilylpropargyl-4-nitrophenylcarbonate. ii: Dess

NAA-modified DNA oligonucleotides with zwitterionic backbones: stereoselective synthesis of A–T phosphoramidite building blocks

• Boris Schmidtgall,
• Claudia Höbartner and
• Christian Ducho

Beilstein J. Org. Chem. 2015, 11, 50–60, doi:10.3762/bjoc.11.8

• some modifications were applied (Scheme 3). Starting from 2'-deoxyadenosine (22), N-6-benzoyl-5'-O-TBDMS-2'-deoxyadenosine (23) was prepared [61] and subjected to oxidation of the 3'-hydroxy functionality to a keto group with Dess–Martin periodinane (DMP). This was followed by reduction with sodium

Palladium-catalysed cyclisation of alkenols: Synthesis of oxaheterocycles as core intermediates of natural compounds

• Miroslav Palík,
• Jozef Kožíšek,
• Peter Koóš and
• Tibor Gracza

Beilstein J. Org. Chem. 2014, 10, 2077–2086, doi:10.3762/bjoc.10.216

• –Martin periodinane, CH2Cl2, 0 °C, 1 h. L-DET = L-dimethyl tartrate. Synthesis of alkenols 24–26 and 28. Reagents and conditions: a) lit. [32] DIBAL-H, CH2Cl2; b) TBDPSCl, imidazole, CH2Cl2, rt, overnight; c) NaH, THF then MeI, rt, overnight; d) FeCl3·6H2O, CHCl3, rt, 1 h (for 25); e) 60% AcOH, 60 °C, 3 h

• ]. Synthesis of alkenols 20-23 and 30. Reagents and conditions: a) lit. [31] (COCl)2, DMSO, Et3N, CH2Cl2, −78 °C to rt, 2 h; b) Phosphonium salt, BuLi, THF, 0 °C to rt, overnight, MPLC; c) lit. [32] (EtO)2POCH2CO2Et, NaH, THF, 0 °C to rt, 3 h; d) 60% AcOH, 60 °C, 3 h; e) MeMgCl, Et2O, 0 °C to rt, 1 h; f) Dess

Syntheses of ¹⁵N-labeled pre-queuosine nucleobase derivatives

• Jasmin Levic and
• Ronald Micura

Beilstein J. Org. Chem. 2014, 10, 1914–1918, doi:10.3762/bjoc.10.199

• work-up and reversed-phase column chromatography (C18) (Scheme 2) [14]. Then, the α-bromo aldehyde 7 was obtained in two steps from commercially available 3-phthalimidopropan-1-ol that was oxidized using Dess–Martin periodinane. Subsequent in situ bromination of the 3-phthalimidopropan-1-al with

• chromatography, 92%. Compound 2 was isolated as salt of trifluoroacetic acid (TFA). Synthesis of [H215N(C7')] preQ1 base (3). a) K2CO3 (1.5 equiv), DMF, 70 °C, 14 h, 47%. b) Dess–Martin periodinane (1.5 equiv), CH2Cl2, 3 h, room temperature. c) 5,5-dibromobarbituric acid (0.6 equiv), acetonitrile, reflux, 2 h

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

• converted to the corresponding sulfonamide with para-methoxyphenyl (PMP) sulfonyl chloride. Cleavage of the silyl ether moiety with TBAF gave primary alcohol 143, which was oxidized to the corresponding acid 144 by a two-step protocol consisting of treatment with Dess–Martin periodinane followed by Pinnick

• primary alcohol of the side chain was oxidized with Dess–Martin periodinane (DMP) to give aldehyde 183. The latter was subsequently reacted with trimethylsilyl ketene acetal 184 in the presence of oxazaborolidinone 185 to afford aldol product 186 and the C22-epimer as only isomers in a 1:1 mixture. Dess