Photovoltaic-driven organic electrosynthesis and efforts toward more sustainable oxidation reactions

• Bichlien H. Nguyen,
• Robert J. Perkins,
• Jake A. Smith and
• Kevin D. Moeller

Beilstein J. Org. Chem. 2015, 11, 280–287, doi:10.3762/bjoc.11.32

• barriers of quaternary carbon and six-membered ring formation. The use of the second nucleophile and a fast initial trapping reaction reduced the cation character of the radical cation intermediate, slowed competitive elimination reactions, and allowed for the desired quaternary carbon formation. In these

Aspergiloid I, an unprecedented spirolactone norditerpenoid from the plant-derived endophytic fungus Aspergillus sp. YXf3

• Zhi Kai Guo,
• Rong Wang,
• Wei Huang,
• Xiao Nian Li,
• Rong Jiang,
• Ren Xiang Tan and
• Hui Ming Ge

Beilstein J. Org. Chem. 2014, 10, 2677–2682, doi:10.3762/bjoc.10.282

• singlet methyl groups’ protons H3-17 and H3-18 to C-3, C-4, and C-5 indicate that C-17 and C-18 were located on the same quaternary carbon C-4, which was connected by C-3 and C-5. HMBC correlations from the hydroxy proton (δH 5.21) to C-5, and C-6 (acquired in DMSO-d6), and from H-5 to C-1, C-6, and C-7

• (acquired in CDCl3) assigned the connectivity of the C-6 to C-1, C-5, and C-7. The other singlet methyl group, C-16, and the terminal vinyl group (C-14–C-15), were also located on the same quaternary carbon, C-10, which was flanked by C-9 and C-11 deduced from the HMBC correlations from H2-9 to C-10, C-11

Formal total syntheses of classic natural product target molecules via palladium-catalyzed enantioselective alkylation

• Yiyang Liu,
• Marc Liniger,
• Ryan M. McFadden,
• Jenny L. Roizen,
• Jacquie Malette,
• Corey M. Reeves,
• Douglas C. Behenna,
• Masaki Seto,
• Jimin Kim,
• Justin T. Mohr,
• Scott C. Virgil and
• Brian M. Stoltz

Beilstein J. Org. Chem. 2014, 10, 2501–2512, doi:10.3762/bjoc.10.261

• construction of building blocks bearing quaternary carbon and fully substituted tertiary centers [1][2]. A recent addition developed by our laboratory is the allylic alkylation of nonstabilized enolate precursors to form α-quaternary carbonyl compounds (Scheme 1) [3]. Once the key stereocenter is set by this

Chiral phosphines in nucleophilic organocatalysis

• Yumei Xiao,
• Zhanhu Sun,
• Hongchao Guo and
• Ohyun Kwon

Beilstein J. Org. Chem. 2014, 10, 2089–2121, doi:10.3762/bjoc.10.218

• (Scheme 48) [91]. The reaction worked efficiently in the presence of 4 Å molecular sieves in toluene at room temperature to furnish a variety of functionalized cyclopentenes bearing quaternary carbon stereocenters in 29–92% yield with 66–98% ee. Unfortunately, the reaction times were long (up to 7 days

Reaction of selected carbohydrate aldehydes with benzylmagnesium halides: benzyl versus o-tolyl rearrangement

• Maroš Bella,
• Bohumil Steiner,
• Vratislav Langer and
• Miroslav Koóš

Beilstein J. Org. Chem. 2014, 10, 1942–1950, doi:10.3762/bjoc.10.202

• spectroscopy (gCOSY, gTOCSY, gHSQCAD, gHMBCAD, and gH2BC) including 1D sequences with selective excitations (1DNOESY, 1DTOCSY, and 1DROESY) were used for the signal assignments. The quaternary carbon atoms were identified on the basis of a semi-selective INEPT experiment and a 1D INADEQUATE pulse sequence

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

• a branching unit (TRIS) at the G(1) level. Thus, compounds 12, 17, and 21 differ by having nine atoms between the anomeric carbon and the focal quaternary carbon of TRIS followed by two, four, and nine atoms to reach the benzene carbon, respectively (~4, 6, and 12 Å). Finally, the synthesis of a 27

Silver and gold-catalyzed multicomponent reactions

• Giorgio Abbiati and
• Elisabetta Rossi

Beilstein J. Org. Chem. 2014, 10, 481–513, doi:10.3762/bjoc.10.46

• corresponding propargylamines 7 containing a quaternary carbon center [37] (Scheme 8). Aliphatic alkynes and acyclic amines gave the corresponding products in low yields, whereas the methodology was ineffective for aromatic ketones. Gold-catalyzed A3-MCRs were also applied with the aim to functionalize

Decandrinin, an unprecedented C₉-spiro-fused 7,8-seco-ent-abietane from the Godavari mangrove Ceriops decandra

• Hui Wang,
• Min-Yi Li,
• Félix Zongwe Katele,
• Tirumani Satyanandamurty,
• Jun Wu and
• Gerhard Bringmann

Beilstein J. Org. Chem. 2014, 10, 276–281, doi:10.3762/bjoc.10.23

• carbonyl carbon (δC 170.9) of a δ-lactone suggested its location at C-7, while those from H2-11, H-14, and H3-20 to the quaternary carbon (δC 88.3) placed it at C-9 (Figure 2). The NOE interactions for the two methyl groups at C-4 suggested that one methyl group is located at the same side as H-5, while

Tanzawaic acids I–L: Four new polyketides from Penicillium sp. IBWF104-06

• Louis P. Sandjo,
• Eckhard Thines,
• Till Opatz and
• Anja Schüffler

Beilstein J. Org. Chem. 2014, 10, 251–258, doi:10.3762/bjoc.10.20

• with only one CH3 group appearing as a doublet at δH 0.98 (d, J = 6.2 Hz, H-18)/δC 23.4. The second CH3 group observed as a doublet in compounds 1–3 appeared in the 1H NMR spectrum of 4 as a singlet (δH 1.20, H-17) and showed a HMBC correlation with the quaternary carbon at δC 70.1 (C-10) (Figure 4

Plakilactones G and H from a marine sponge. Stereochemical determination of highly flexible systems by quantitative NMR-derived interproton distances combined with quantum mechanical calculations of ¹³C chemical shifts

• Simone Di Micco,
• Angela Zampella,
• Maria Valeria D’Auria,
• Carmen Festa,
• Simona De Marino,
• Raffaele Riccio,
• Craig P. Butts and
• Giuseppe Bifulco

Beilstein J. Org. Chem. 2013, 9, 2940–2949, doi:10.3762/bjoc.9.331

• oxygenated carbons and one acyl group. The acyl carbon signal at 175.9 ppm (C-1), along with the oxygenated carbon resonance at δC 91.9 (C-4) suggested the presence of a lactone. The olefinic methine carbon at δC 153.5 (C-3) with the quaternary carbon at δC 136.6 (C-2) completed the five-membered α,β

SF002-96-1, a new drimane sesquiterpene lactone from an Aspergillus species, inhibits survivin expression

• Silke Felix,
• Louis P. Sandjo,
• Till Opatz and
• Gerhard Erkel

Beilstein J. Org. Chem. 2013, 9, 2866–2876, doi:10.3762/bjoc.9.323

• contact with methylene protons at δ 1.57 and 1.66 while the latter presented the same correlation with methylene protons at δ 1.34 and 1.37. The protons of two geminal methyl groups (δ 0.97, 1.15) displayed HBMC correlations with the methine carbon at δ 45.7, a quaternary carbon at δ 34.0 and the

The myxocoumarins A and B from Stigmatella aurantiaca strain MYX-030

• Tobias A. M. Gulder,
• Snežana Neff,
• Traugott Schüz,
• Tammo Winkler,
• René Gees and
• Bettina Böhlendorf

Beilstein J. Org. Chem. 2013, 9, 2579–2585, doi:10.3762/bjoc.9.293

• ). These signals were assigned to three methyl groups (14.0, 16.5, and 21.2 ppm), eight methylene units (22.6, 23.4, 29.2, 29.3, 29.4, 29.8, 31.8, and 38.3 ppm), a quaternary carbon at 46.5 ppm, a heteroatom-substituted quaternary carbon – most likely a tertiary alcohol – at 79.1 ppm, an ester-type

• groups to each other, to the putative ester functionality, the quaternary carbon at 46.5 ppm, and the tertiary alcohol carbon at 79.1 ppm led to the assembly of structural fragment II (F-II, Figure 2). Further substitution of the latter was obvious from HMBC cross peaks of the diastereotopic CH2 group

Gold(I)-catalyzed enantioselective cycloaddition reactions

• Fernando López and
• José L. Mascareñas

Beilstein J. Org. Chem. 2013, 9, 2250–2264, doi:10.3762/bjoc.9.264

• allowed the preparation of cyclobutanes 20 containing challenging quaternary carbon centers (Scheme 12). From a mechanistic point of view, these [2 + 2] cycloadditions, either in racemic or asymmetric versions, have been proposed to proceed through a stepwise cationic pathway consisting of an initial

Asymmetric allylic alkylation of Morita–Baylis–Hillman carbonates with α-fluoro-β-keto esters

• Lin Yan,
• Zhiqiang Han,
• Bo Zhu,
• Caiyun Yang,
• Choon-Hong Tan and
• Zhiyong Jiang

Beilstein J. Org. Chem. 2013, 9, 1853–1857, doi:10.3762/bjoc.9.216

• nucleophiles, have been successfully developed. A series of important fluorinated adducts, with chiral quaternary carbon centres containing a fluorine atom, was achieved in good yields (up to 93%), with good to excellent enantioselectivities (up to 96% ee) and moderate diastereoselectivities (up to 4:1 dr

• enantioselectivities [38]. Notably, the reaction between an achiral fluorocarbon nucleophile with MBH carbonates, to afford compounds with chiral quaternary carbon centres bearing a fluorine atom, remains a formidable task. Since 2009, we developed a highly enantioselective and diastereoselective guanidine-catalyzed

• compounds with chiral quaternary carbon centres containing a fluorine atom. Results and Discussion In the preliminary experiments, we investigated the reaction of α-fluoro-β-ketoester 1a with MBH carbonate 2a as the model substrate, in the presence of several commercially available Cinchona alkaloids as

Organocatalyzed enantioselective desymmetrization of aziridines and epoxides

• Ping-An Wang

Beilstein J. Org. Chem. 2013, 9, 1677–1695, doi:10.3762/bjoc.9.192

• producing γ-amino acid derivatives with one stereogenic quaternary carbon has been independently developed by Dixon [42] and Jørgensen’s group [43]. Dixon and co-workers discovered that OC-16 bearing bulky substituents both on the 9-O atom and the bridgehead nitrogen afforded excellent enantioselectivity of

A construction of 4,4-spirocyclic γ-lactams by tandem radical cyclization with carbon monoxide

• Mitsuhiro Ueda,
• Yoshitaka Uenoyama,
• Nozomi Terasoma,
• Shoko Doi,
• Shoji Kobayashi,
• Ilhyong Ryu and
• John A. Murphy

Beilstein J. Org. Chem. 2013, 9, 1340–1345, doi:10.3762/bjoc.9.151

• ; iodoaryl allyl azides; tandem radical cyclization; Introduction 4,4-Spirocyclic oxindole γ-lactams containing a quaternary carbon center are key structures for the synthesis of biologically active natural products and the related analogues [1][2][3][4]. Therefore, the development of an efficient synthesis

Lanostane- and cycloartane-type triterpenoids from Abies balsamea oleoresin

• Serge Lavoie,
• Charles Gauthier,
• Jean Legault,
• Sylvain Mercier,
• Vakhtang Mshvildadze and
• André Pichette

Beilstein J. Org. Chem. 2013, 9, 1333–1339, doi:10.3762/bjoc.9.150

• methylene and three sp3 methine groups, three sp3 quaternary carbon atoms, one sp2 methylene and three sp2 methine groups, and seven sp2 quaternary carbon atoms. A 1H–1H COSY experiment provided correlations from H2-1 to H2-2, H-6 to H-5 and H-7, H2-11 to H-9 and H2-12, H2-15 to H2-16 and H-20 to H3-21 and

Cascade radical reaction of substrates with a carbon–carbon triple bond as a radical acceptor

• Hideto Miyabe,
• Ryuta Asada and
• Yoshiji Takemoto

Beilstein J. Org. Chem. 2013, 9, 1148–1155, doi:10.3762/bjoc.9.128

• stereoselectively. Particularly, the substrate 16 having a phenyl group gave the intermediate linear π-radical. Thus, the capture of linear vinyl radical with atom-transfer reagent would be influenced by the steric hindrance around the quaternary carbon atom [43]. Conclusion We have shown the cascade radical

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

• synthesis; C2-symmetry; catalysis; Diels–Alder reaction; Lewis acid; natural product; quaternary carbon; Introduction Ryanodine (Scheme 1) [1][2][3] is a potent modulator of the intracellular calcium release channels, known as ryanodine receptors [4][5]. Its complex architecture, including eight contiguous

Palladium-catalyzed dual C–H or N–H functionalization of unfunctionalized indole derivatives with alkenes and arenes

• Gianluigi Broggini,
• Egle M. Beccalli,
• Andrea Fasana and
• Silvia Gazzola

Beilstein J. Org. Chem. 2012, 8, 1730–1746, doi:10.3762/bjoc.8.198

• elimination. Palladium–pyridine systems were subsequently investigated with chiral ligands to catalyze enantioselective processes involving alkenylindoles. Several enantioselective indole annulations with formation of a stereogenic quaternary carbon atom were performed by using chiral oxazoline ligands with

Carbohydrate-auxiliary assisted preparation of enantiopure 1,2-oxazine derivatives and aminopolyols

• Marcin Jasiński,
• Dieter Lentz and
• Hans-Ulrich Reissig

Beilstein J. Org. Chem. 2012, 8, 662–674, doi:10.3762/bjoc.8.74

• quaternary carbon atoms in the 13C NMR spectrum evidenced the presence of the pyrrole structure. Finally, the HMBC experiment proved the proposed substitution pattern at the pyrrole ring. HRMS and elemental analysis allowed identification of 5 as a 2,3,4,5-tetrasubstituted pyrrole derivative. As shown in

Marilones A–C, phthalides from the sponge-derived fungus Stachylidium sp.

• Celso Almeida,
• Stefan Kehraus,
• Miguel Prudêncio and
• Gabriele M. König

Beilstein J. Org. Chem. 2011, 7, 1636–1642, doi:10.3762/bjoc.7.192

• correlations from 9’-H3 to C-2’, C-3’ and C-4’, and from methyl protons 8’-H3 and 10’-H3 to C-6’and C-7’, disclosing a geranyl fragment. Based on literature comparisons we established the configuration of Δ2’/3’ as E [11]. The aromatic quaternary carbon C-5 (δC 164.2) had a carbon resonance that indicated a

Translation of microwave methodology to continuous flow for the efficient synthesis of diaryl ethers via a base-mediated S_NAr reaction

• Charlotte Wiles and
• Paul Watts

Beilstein J. Org. Chem. 2011, 7, 1360–1371, doi:10.3762/bjoc.7.160

• spectra obtained were consistent with the literature. The following abbreviations are used to report NMR spectroscopic data; s = singlet, d = doublet, t = triplet, br s = broad singlet, q = quartet, dd = double doublet, dt = doublet of triplets, m = multiplet and C0 = quaternary carbon. Analysis of

One-pot Diels–Alder cycloaddition/gold(I)-catalyzed 6-endo-dig cyclization for the synthesis of the complex bicyclo[3.3.1]alkenone framework

• Boubacar Sow,
• Gabriel Bellavance,
• Francis Barabé and
• Louis Barriault

Beilstein J. Org. Chem. 2011, 7, 1007–1013, doi:10.3762/bjoc.7.114

• Boubacar Sow Gabriel Bellavance Francis Barabe Louis Barriault Department of Chemistry, 10 Marie Curie, University of Ottawa, Ottawa, Canada, K1N 6N5 10.3762/bjoc.7.114 Abstract The rapid synthesis of bicyclo[m.n.1]alkanone cores possessing quaternary carbon centers adjacent to a bridged ketone

When gold can do what iodine cannot do: A critical comparison

• Sara Hummel and
• Stefan F. Kirsch

Beilstein J. Org. Chem. 2011, 7, 847–859, doi:10.3762/bjoc.7.97

• stereocenters, including a quaternary carbon. As in the previous examples, the gold-catalyzed cyclization benefits strongly from a stabilizing substituent at C2 to direct the 6-endo mode of cyclization. Subsequent to the success of the gold-catalyzed cycloisomerization in trapping the developing carbocation