Total synthesis of the endogenous inflammation resolving lipid resolvin D2 using a common lynchpin

• John Li,
• May May Leong,
• Alastair Stewart and
• Mark A. Rizzacasa

Beilstein J. Org. Chem. 2013, 9, 2762–2766, doi:10.3762/bjoc.9.310

• the ylide derived from 9 provided the alkene 10 [9] with excellent stereoselectivity. Oxidation of 10 with Dess–Martin periodinane then afforded aldehyde 7. The phosphonium salt 6 [21][22] was produced from propargyl bromide via silylation of the derived sodium salt with TIPSCl followed by reaction

Multigramme synthesis and asymmetric dihydroxylation of a 4-fluorobut-2E-enoate

• James A. B. Laurenson,
• John A. Parkinson,
• Jonathan M. Percy,
• Giuseppe Rinaudo and
• Ricard Roig

Beilstein J. Org. Chem. 2013, 9, 2660–2668, doi:10.3762/bjoc.9.301

• one-pot oxidation/Wittig procedure was implemented from 37a; treatment with the Dess–Martin periodinane [41] in the presence of the stabilised ylide afforded a 4:1 E:Z mixture of the product alkene 39a in good (74%) yield. A second purification by column chromatography isolated the E-alkene

The total synthesis of D-chalcose and its C-3 epimer

• Jun Sun,
• Song Fan,
• Zhan Wang,
• Guoning Zhang,
• Kai Bao and
• Weige Zhang

Beilstein J. Org. Chem. 2013, 9, 2620–2624, doi:10.3762/bjoc.9.296

• via TBSOTf to furnish 11, and 11 could be converted into 12 (Scheme 5). With requisite intermediate 12 in hand, our attention was directed toward preparing the final product, chalcose. Alcohol 12 was subjected to Dess–Martin periodinane [29] because it afforded aldehyde 13 in 86% yield, making it

• form 7′ using TBSOTf. Alcohol 8′ was oxidized using Dess–Martin periodinane to give aldehyde 9′ in 86% yield. Finally, 9′ was efficiently deprotected with TBAF, leading to the C-3 epimer of chalcose (I′) in 83% yield. Epimer I′ was acetylated using acetic anhydride in pyridine, furnishing diacetate 10

• -toluenesulfonate. Reagents and conditions: (a) TBSOTf, 2,6-lutidine, CH2Cl2, rt, 90%; (b) CSA, MeOH, 0 °C, 59%. TBS = t-butyldimethylsilyl, Tf = trifluoromethanesulfonyl, CSA = DL-10-camphorsulfonic acid. Reagents and conditions: (a) Dess–Martin periodinane, CH2Cl2, rt, 86%; (b) TBAF, THF, 0 °C, 84%; (c) Py, AcO2

Towards stereochemical control: A short formal enantioselective total synthesis of pumiliotoxins 251D and 237A

• Jie Zhang,
• Hong-Kui Zhang and
• Pei-Qiang Huang

Beilstein J. Org. Chem. 2013, 9, 2358–2366, doi:10.3762/bjoc.9.271

• alcohol 22 was investigated. Oxidation of alcohol 18 with an excess of Dess–Martin periodinane (DMP) in dichloromethane at room temperature for 2 h proceeded smoothly to give ketone 10 in 93% yield. It is noteworthy that keto-lactam 10 is configurational labile, and should be used immediately in the next

• . (S)-6-(But-3-en-1-yl)-1-(4-methoxybenzyl)piperidine-2,5-dione (10): To a stirred solution of compound 18 (100 mg, 0.34 mmol) in CH2Cl2 (5 mL) was added Dess–Martin periodinane (220 mg, 0.52 mmol) at room temperature. After being stirred for 2 h, the reaction was quenched with a 10% aqueous solution

The chemistry of isoindole natural products

• Klaus Speck and
• Thomas Magauer

Beilstein J. Org. Chem. 2013, 9, 2048–2078, doi:10.3762/bjoc.9.243

• (52) and cytochalasin L-696,474 (78) diverged. For 78, another five steps were necessary to form the isoindolinone 74. After oxidation of the primary alcohol with Dess–Martin periodinane, the obtained aldehyde was coupled with the readily available N-phenyltetrazole sulfone 75 via a Julia–Kocienski

An approach towards azafuranomycin analogs by gold-catalyzed cycloisomerization of allenes: synthesis of (αS,2R)-(2,5-dihydro-1H-pyrrol-2-yl)glycine

• Jörg Erdsack and
• Norbert Krause

Beilstein J. Org. Chem. 2013, 9, 1936–1942, doi:10.3762/bjoc.9.229

• ] (Scheme 4). This protection step was carried out in order to avoid dehydrogenation or chlorination of the secondary amine in the subsequent oxidation steps [64][65]. Acetal cleavage under mild protic conditions furnished the hydroxycarbamate, which underwent two-step oxidation with Dess–Martin periodinane

ML212: A small-molecule probe for investigating fluconazole resistance mechanisms in Candida albicans

• Willmen Youngsaye,
• Cathy L. Hartland,
• Barbara J. Morgan,
• Amal Ting,
• Partha P. Nag,
• Benjamin Vincent,
• Carrie A. Mosher,
• Joshua A. Bittker,
• Sivaraman Dandapani,
• Michelle Palmer,
• Luke Whitesell,
• Susan Lindquist,
• Stuart L. Schreiber and
• Benito Munoz

Beilstein J. Org. Chem. 2013, 9, 1501–1507, doi:10.3762/bjoc.9.171

• bromoacetate, K2CO3, acetone, 60 °C; (d) alkylmagnesium bromide, Et2O, 0 °C; (e) Dess–Martin periodinane, CH2Cl2; (f) hydrazine hydrate, 175 °C. Activity of substituted indazole cores.a Investigation of 3-substituted indazoles.a Substituent effects associated with the 3-phenyl ring.a Supporting Information

Hypervalent iodine/TEMPO-mediated oxidation in flow systems: a fast and efficient protocol for alcohol oxidation

• Nida Ambreen,
• Ravi Kumar and
• Thomas Wirth

Beilstein J. Org. Chem. 2013, 9, 1437–1442, doi:10.3762/bjoc.9.162

• [4][5][6]. Hypervalent iodine compounds in general have emerged as versatile oxidizing agents with compounds such as DMP (Dess–Martin periodinane) and IBX finding regular utility as highly selective oxidizing agents [7][8][9]. The use of the nitroxyl radical TEMPO (2,2,6,6-tetramethylpiperidine-1

Gold-catalyzed oxycyclization of allenic carbamates: expeditious synthesis of 1,3-oxazin-2-ones

• Benito Alcaide,
• Pedro Almendros,
• M. Teresa Quirós and
• Israel Fernández

Beilstein J. Org. Chem. 2013, 9, 818–826, doi:10.3762/bjoc.9.93

• , rt, 15 h. (vi) Boc2O, DMAP, CH3CN, rt, 2 h. (vii) Dess–Martin periodinane, CH2Cl2, rt. PMP = 4-MeOC6H4. Controlled oxycyclization reactions of allenic carbamates 2 to 1,3-oxazinan-2-ones 3 and 1,3-oxazin-2-ones 4 under selective gold-catalyzed conditions. Reagents and conditions: (i) 2.5 mol

Asymmetric synthesis of a highly functionalized bicyclo[3.2.2]nonene derivative

• Toshiki Tabuchi,
• Daisuke Urabe and
• Masayuki Inoue

Beilstein J. Org. Chem. 2013, 9, 655–663, doi:10.3762/bjoc.9.74

• without further purification. A mixture of the above crude alcohol, NaHCO3 (33 mg, 0.39 mmol), and Dess–Martin periodinane (53 mg, 0.13 mmol) in CH2Cl2 (0.8 mL) was stirred at room temperature for 2.5 h, and then saturated aqueous Na2S2O3 (3 mL) was added. The resultant mixture was extracted with Et2O (4

The crystal structure of the Dess–Martin periodinane

• Albert Schröckeneder,
• Desiree Stichnoth,
• Peter Mayer and
• Dirk Trauner

Beilstein J. Org. Chem. 2012, 8, 1523–1527, doi:10.3762/bjoc.8.172

• the Dess–Martin periodinane (DMP), a hypervalent iodine reagent popular amongst synthetic chemists. In the solid state, the highly crystalline compound forms an intricate coordination polymer held together by intermolecular halogen and hydrogen bonds. Keywords: crystal structure; Dess–Martin

• periodinane; halogen bonds; hypervalent iodine; oxidant; Introduction The so-called Dess–Martin periodinane (DMP, 1,1,1-triacetoxy-1,1-dihydro-1,2-benziodoxol-3(1H)-one, 1) has emerged as one of the most useful reagents for the oxidation of primary and secondary alcohols to the corresponding aldehydes and

• , however, no π-stacking interactions. Least-square planes of the four oxygen atoms bound covalently to iodine are nearly parallel to the c-axis (deviation angle 0.79(4)°). Conclusion In conclusion, we have determined the solid-state structure of the Dess–Martin periodinane (1), a popular reagent in organic

A straightforward approach towards combined α-amino and α-hydroxy acids based on Passerini reactions

• Ameer F. Zahoor,
• Sarah Thies and
• Uli Kazmaier

Beilstein J. Org. Chem. 2011, 7, 1299–1303, doi:10.3762/bjoc.7.151

• at the sterically least-hindered position [26]. These alcohols can easily be oxidized by Swern-oxidation [27] or with Dess–Martin-periodinane (DMP) [28], giving rise to the required γ-oxo-amino acids 2 (Table 1). In principle both protocols are suitable for oxidation, but in general the yields

Isotopic labelling studies for a gold-catalysed skeletal rearrangement of alkynyl aziridines

• Paul W. Davies,
• Nicolas Martin and
• Neil Spencer

Beilstein J. Org. Chem. 2011, 7, 839–846, doi:10.3762/bjoc.7.96

• . Working mechanism to rationalise the formation of two regiosomeric pyrroles in the gold catalysed cycloisomerisation of alkynyl aziridines. Bond fissions featured in the proposed mechanistic hypothesis and the initial mechanism probe. Preparation of D-labelled alkynyl aziridine 4. DMP = Dess–Martin

• periodinane. Reaction of deuterated alkynyl aziridine 4 in the skeletal rearrangement reaction. Preparation of 13C-enriched alkynyl aziridines. Cycloisomerisation of 11 in the skeletal rearrangement reaction. Cycloisomerisation of 11 to give 2,5-disubstituted pyrrole. Cycloisomerisation of 14 in the skeletal

Application of the diastereoselective photodeconjugation of α,β-unsaturated esters to the synthesis of gymnastatin H

• Ludovic Raffier and
• Olivier Piva

Beilstein J. Org. Chem. 2011, 7, 151–155, doi:10.3762/bjoc.7.21

• the corresponding allylic alcohol 22 followed by the oxidation with Dess–Martin periodinane (DMP) [21] afforded aldehyde 23 which was converted into the known ethyl ester (E,E)-24 by a subsequent Wittig–Horner reaction. The comparison of the optical rotation with literature data confirmed the (R

Facile synthesis of two diastereomeric indolizidines corresponding to the postulated structure of alkaloid 5,9E- 259B from a Bufonid toad (Melanophryniscus)

• Angela Nelson,
• H. Martin Garraffo,
• Thomas F. Spande,
• John W. Daly and
• Paul J. Stevenson

Beilstein J. Org. Chem. 2008, 4, No. 6, doi:10.1186/1860-5397-4-6

• 5,9E-259B, and b) synthetic 7. Structure shown with relative configuration. Reagents: (i) MeMgI. 96% (ii) PTSA 71%. (iii) TiCl4 CH2Cl2 25 oC 3d 68%. (iv) MsCl, Et3N, THF -40 oC, 74%. (v) Grubbs' catalyst, 25 oC CH2Cl2, 90%. (vi) H2 MeOH Pt/C 79%. (vii) LiAlH4, AlCl3, 73%. (viii) (a) Dess Martin

• periodinane, 77%. (b) Ph3P+CH2I I-, NaN(SiMe3)2 51%. (c) TMS acetylene, CuI, Pd(Ph3P)3, Et3N then K2CO3 MeOH, 69%. Supporting Information Supporting Information File 28: Experimental. Details of experimental procedures and data for characterisation of new compounds. Acknowledgements We would like to thank

Flexible synthetic routes to poison- frog alkaloids of the 5,8-disubstituted indolizidine- class I: synthesis of common lactam chiral building blocks and application to the synthesis of (-)-203A, (-)-205A, and (-)-219F

• Naoki Toyooka,
• Dejun Zhou,
• Hideo Nemoto,
• H. Martin Garraffo,
• Thomas F. Spande and
• John W. Daly

Beilstein J. Org. Chem. 2007, 3, No. 29, doi:10.1186/1860-5397-3-29

• , followed by an Arndt-Eistert sequence of the resulting carboxylic acid. Reduction of both carbonyl groups in 14 with lithium aluminum hydride provided the alcohol, which was directly used for formation of Z-iodoolefin 15. Thus, the Dess-Martin periodinane oxidation [24] of the alcohol, followed by Wittig

Tether- directed synthesis of highly substituted oxasilacycles via an intramolecular allylation employing allylsilanes

• Peter J. Jervis and
• Liam R. Cox

Beilstein J. Org. Chem. 2007, 3, No. 6, doi:10.1186/1860-5397-3-6

• temperature, allowing further reduction to the corresponding primary alcohols. Fortunately, the two alcohol products could be oxidised to the desired aldehydes syn-4a and anti-4a, using Dess-Martin periodinane[22][23] without epimerisation of the α-stereogenic centre (Scheme 7). With all four cyclisation