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

• derivative, 2-dimethoxybenzoate 20 was prepared from tribenzylated ribose 16. Introduction of a dimethoxybenzoyl (DMBz) group at the 2-position and diastereoselective formation of sulfoxide 20, favored in Pummerer-type glycosylation reactions and cases where the approach of the nucleophile is restricted

Three-component coupling of aryl iodides, allenes, and aldehydes catalyzed by a Co/Cr-hybrid catalyst

• Kimihiro Komeyama,
• Shunsuke Sakiyama,
• Kento Iwashita,
• Itaru Osaka and
• Ken Takaki

Beilstein J. Org. Chem. 2018, 14, 1413–1420, doi:10.3762/bjoc.14.118

• iodides, allenes, and aldehydes has been developed to afford multi-substituted homoallylic alcohols in a diastereoselective manner. Control experiments for understanding the reaction mechanism reveal that the cobalt catalyst is involved in the oxidative addition and carbometalation steps in the reaction

• , whereas the chromium salt generates highly nucleophilic allylchromium intermediates from allylcobalt species, without the loss of stereochemical information, to allow the addition to aldehydes. Keywords: chromium; cobalt; diastereoselective; homoallyl alcohols; hybrid catalyst; three-component coupling

• three-component coupling method is herein reported for the direct synthesis of highly diastereoselective multi-substituted homoallyl alcohols employing a cobalt/chromium hybrid catalyst (Scheme 5). Results and Discussion Initially, suitable reaction conditions were investigated for the three-component

Recent applications of chiral calixarenes in asymmetric catalysis

• Mustafa Durmaz,
• Erkan Halay and
• Selahattin Bozkurt

Beilstein J. Org. Chem. 2018, 14, 1389–1412, doi:10.3762/bjoc.14.117

• to synthesize inherently chiral calixarenes 36 and 37 [43][44]. In a continuation of their previous studies, they have reported diastereoselective synthesis of inherently chiral calixarene derivatives 38 and 39 via chiral tert-butyloxazoline-directed lithiation (Figure 4) [45]. It has been shown that

Stereoselective nucleophilic addition reactions to cyclic N-acyliminium ions using the indirect cation pool method: Elucidation of stereoselectivity by spectroscopic conformational analysis and DFT calculations

• Koichi Mitsudo,
• Junya Yamamoto,
• Tomoya Akagi,
• Atsuhiro Yamashita,
• Masahiro Haisa,
• Kazuki Yoshioka,
• Hiroki Mandai,
• Koji Ueoka,
• Christian Hempel,
• Jun-ichi Yoshida and
• Seiji Suga

Beilstein J. Org. Chem. 2018, 14, 1192–1202, doi:10.3762/bjoc.14.100

• give the disubstituted piperidine derivatives in an excellent diastereoselective manner (Scheme 1). This result inspired us to investigate the stereochemistry of the N-acyliminium ions by means of NMR spectroscopy, which is challenging to achieve without using cation pool methods. The current report

• presents the diastereoselective synthesis of disubstituted piperidine derivatives by the indirect cation pool method and the elucidation of the stereoselectivity based on both NMR analyses of the cyclic N-acyliminium ions and DFT calculations. Results and Discussion N-Acyliminium ions obtained from N-Boc

• form product, because an attack from another side would lead to a more unstable product with a twist form [13]. As a close study, Woerpel reported a diastereoselective substitution reaction for synthesizing disubstituted tetrahydropyrans via six-membered oxocarbenium ions generated in situ from

Fluorocyclisation via I(I)/I(III) catalysis: a concise route to fluorinated oxazolines

• Felix Scheidt,
• Christian Thiehoff,
• Gülay Yilmaz,
• Stephanie Meyer,
• Constantin G. Daniliuc,
• Gerald Kehr and
• Ryan Gilmour

Beilstein J. Org. Chem. 2018, 14, 1021–1027, doi:10.3762/bjoc.14.88

• diastereoselective on account of the proximal nature of the stereocentre (65%, dr >95:5). Compound 3 is noteworthy on account of the β-amino alcohol and β-fluoro alcohol motifs that collectively preorganised the propyl chain. Stabilising hyperconjugative interactions manifest themselves in the characteristic gauche

Diastereoselective auxiliary- and catalyst-controlled intramolecular aza-Michael reaction for the elaboration of enantioenriched 3-substituted isoindolinones. Application to the synthesis of a new pazinaclone analogue

• Romain Sallio,
• Stéphane Lebrun,
• Frédéric Capet,
• Francine Agbossou-Niedercorn,
• Christophe Michon and
• Eric Deniau

Beilstein J. Org. Chem. 2018, 14, 593–602, doi:10.3762/bjoc.14.46

• stereocenter [14]. Hence, the asymmetric synthesis of functionalized 3-substituted isoindolinones using short, versatile and selective procedures is clearly a topic of current interest. Two strategies can be applied for the asymmetric synthesis of 3-substituted isoindolinones. First, diastereoselective

• and 8 in 61–75% isolated yields after work-up (Scheme 2, Figure 3). Diastereoselective intramolecular aza-Michael reaction First, the study of the diastereoselective intramolecular aza-Michael reaction of benzamide substrate (S)-6a allowed us to optimize the reaction conditions (Table 1) and latter to

• 3:7). Removal of the chiral auxiliary. Synthesis of isoindolinones 1a–c, 1e, 2; isolated yield, ee by HPLC. Synthesis of pazinaclone analogue (3S)-27. Identification of the optimum reaction conditions for the diastereoselective intramolecular aza-Michael reaction of (S)-6a. Identification of the

The selective electrochemical fluorination of S-alkyl benzothioate and its derivatives

• Shunsuke Kuribayashi,
• Tomoyuki Kurioka,
• Shinsuke Inagi,
• Ho-Jung Lu,
• Biing-Jiun Uang and
• Toshio Fuchigami

Beilstein J. Org. Chem. 2018, 14, 389–396, doi:10.3762/bjoc.14.27

• be the most suitable combination as electrolytic solvent and supporting salt as well as fluorine source for the anodic fluorination. The electrochemical fluorination of cyclic benzothioates such as benzothiophenone was also achieved. Keywords: anodic cyclization; diastereoselective fluorination

Syn-selective silicon Mukaiyama-type aldol reactions of (pentafluoro-λ⁶-sulfanyl)acetic acid esters with aldehydes

• Anna-Lena Dreier,
• Andrej V. Matsnev,
• Joseph S. Thrasher and
• Günter Haufe

Beilstein J. Org. Chem. 2018, 14, 373–380, doi:10.3762/bjoc.14.25

• rearrangement [31]. Under slightly modified conditions, this type of rearrangement was also successful for SF5-substituted acetic esters of cinnamyl alcohols [32]. Herein we describe our results [33] of highly syn-diastereoselective silicon Mukaiyama-type aldol reactions of SF5-acetic acid esters with different

Recent developments in the asymmetric Reformatsky-type reaction

• Hélène Pellissier

Beilstein J. Org. Chem. 2018, 14, 325–344, doi:10.3762/bjoc.14.21

• Helene Pellissier Aix-Marseille Univ, CNRS, Centrale Marseille, iSm2, Marseille, France 10.3762/bjoc.14.21 Abstract This review collects the most important developments in asymmetric Reformatsky-type reactions published since the beginning of 2013, including both diastereoselective methodologies

• enantioselective (aza)-variants by using chiral substrates or chiral ligands. As illustrated in this review, the diastereoselective Reformatsky reactions of chiral substrates or auxiliaries have been applied to the total synthesis of a number of important products, such as naturally occurring bioactive products

• Reformatsky-type reactions published since the beginning of 2013, since this field was most recently reviewed this year by Colobert for the diastereoselective version [4], and Fernández-Ibáñez and Maciá for the catalytic enantioselective version [5]. Earlier, this field was reviewed by different groups [6][7

Nucleophilic fluoroalkylation/cyclization route to fluorinated phthalides

• Masanori Inaba,
• Tatsuya Sakai,
• Shun Shinada,
• Tsuyuka Sugiishi,
• Yuta Nishina,
• Norio Shibata and
• Hideki Amii

Beilstein J. Org. Chem. 2018, 14, 182–186, doi:10.3762/bjoc.14.12

• asymmetric synthesis of 3-(trifluoromethyl)phthalide (1a) using a chiral auxiliary was published to date. In 2006, Pedrosa and co-workers discribed the diastereoselective nucleophilic trifluoromethylation of aldehyde 5, which was prepared by condensation of ortho-phthalaldehyde with (−)-8-benzylaminomenthol

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

• . However, performing the reaction in the presence of 10 mol % of the catalyst for 40 h drove the reaction to completion. Intriguingly, the ring-closing metathesis proceeded in a highly diastereoselective manner and produced the corresponding cyclized adduct 4a as a single isomer [26]. Finally, with

Quinone-catalyzed oxidative deformylation: synthesis of imines from amino alcohols

• Xinyun Liu,
• Johnny H. Phan,
• Benjamin J. Haugeberg,
• Shrikant S. Londhe and
• Michael D. Clift

Beilstein J. Org. Chem. 2017, 13, 2895–2901, doi:10.3762/bjoc.13.282

• resulting imines (7r−t) are hydrolyzed under the current reaction conditions. Notably, imines 7n [42][43][44][45] and 7t [46][47][48] are useful imines for diastereoselective 1,2-addition reactions. Following these substrate scope studies, we next examined the quinone-catalyzed C–C bond cleavage of

The synthesis of the 2,3-difluorobutan-1,4-diol diastereomers

• Robert Szpera,
• Nadia Kovalenko,
• Kalaiselvi Natarajan,
• Nina Paillard and
• Bruno Linclau

Beilstein J. Org. Chem. 2017, 13, 2883–2887, doi:10.3762/bjoc.13.280

• Robert Szpera Nadia Kovalenko Kalaiselvi Natarajan Nina Paillard Bruno Linclau Chemistry, University of Southampton, Highfield, Southampton SO17 1BJ, United Kingdom 10.3762/bjoc.13.280 Abstract The diastereoselective synthesis of fluorinated building blocks that contain chiral fluorine

A Brønsted base-promoted diastereoselective dimerization of azlactones

• Danielle L. J. Pinheiro,
• Gabriel M. F. Batista,
• Pedro P. de Castro,
• Leonã S. Flores,
• Gustavo F. S. Andrade and
• Giovanni W. Amarante

Beilstein J. Org. Chem. 2017, 13, 2663–2670, doi:10.3762/bjoc.13.264

• Brønsted base system for the diastereoselective dimerization of azlactones using trichloroacetate salts and acetonitrile has been developed. Desired products were obtained in good yields (60–93%) and with up to >19:1 dr after one hour of reaction. Additionally, the relative stereochemistry of the major

• dimer was assigned as being trans, by X-ray crystallographic analysis. The kinetic reaction profile was determined by using 1H NMR reaction monitoring and revealed a second order overall kinetic profile. Furthermore, by employing this methodology, a diastereoselective total synthesis of a functionalized

• bond formation, such as a dimerization process. We herein report a diastereoselective dimerization of azlactones using potassium or sodium trichloroacetate salts and acetonitrile as solvent. Besides, a reaction mechanism is proposed based on NMR studies and the relative stereochemistry of the major

Recent progress in the racemic and enantioselective synthesis of monofluoroalkene-based dipeptide isosteres

• Myriam Drouin and
• Jean-François Paquin

Beilstein J. Org. Chem. 2017, 13, 2637–2658, doi:10.3762/bjoc.13.262

• Boc-Tyr-ψ[(Z)-CF=CH]-Gly using a diastereoselective Reformatsky–Honda condensation, a (E)-selective HWE olefination and a SmI2 reduction as key steps (Scheme 12) [41]. First, Reformatsky–Honda reaction of TIPS-protected phenylacetaldehyde 57 with the chiral auxiliary (L)-phenylglycine derivative 58

• cyclopentanone 90. A HWE olefination converted 90 into (Z)-monofluoroalkene 91 without any significant selectivity. The chiral Ellman’s sulfinylimine 92 was obtained in 3 steps. The diastereoselective addition of isopropyllithium was then possible to afford the (L)-Leu residue with a moderate selectivity (dr

• -ψ[(Z)-CF=CH]-Phe by Dory and co-workers. Diastereoselective addition of Grignard reagents to sulfinylamines derived from α-fluoroenals by Pannecoucke and co-workers. NHC-mediated synthesis of monofluoroalkenes by Otaka and co-workers. Stereoselective synthesis of Boc-Tyr-ψ[(Z)-CF=CH]-Gly by Altman

Synthesis of 1,3-cis-disubstituted sterically encumbered imidazolidinone organocatalysts

• Jan Wallbaum and
• Daniel B. Werz

Beilstein J. Org. Chem. 2017, 13, 2577–2583, doi:10.3762/bjoc.13.254

• accessible from amino acids, are widely used in these kinds of reactions [13][14][15][16][17][18]. More recent examples demonstrate the applicability in various reactions like diastereoselective α-fluorination [19], total syntheses [20][21], cross-dehydrogenative couplings [22], selectivity-reversed Friedel

Diastereoselective Mannich reactions of pseudo-C₂-symmetric glutarimide with activated imines

• Tatsuya Ishikawa,
• Tomoko Kawasaki-Takasuka,
• Toshio Kubota and
• Takashi Yamazaki

Beilstein J. Org. Chem. 2017, 13, 2473–2477, doi:10.3762/bjoc.13.244

Asymmetric synthesis of propargylamines as amino acid surrogates in peptidomimetics

• Matthias Wünsch,
• David Schröder,
• Tanja Fröhr,
• Lisa Teichmann,
• Sebastian Hedwig,
• Nils Janson,
• Clara Belu,
• Jasmin Simon,
• Shari Heidemeyer,
• Philipp Holtkamp,
• Jens Rudlof,
• Lennard Klemme,
• Alessa Hinzmann,
• Beate Neumann,
• Hans-Georg Stammler and
• Norbert Sewald

Beilstein J. Org. Chem. 2017, 13, 2428–2441, doi:10.3762/bjoc.13.240

• subsequent Boc protection [21]. Here we report on the diastereoselective synthesis of chiral N-sulfinyl propargylamines with amino acid type “side chains” attached to the propargylic position mediated by Ellman’s auxiliary. Enantiomerically pure amines can be obtained by condensation of aldehydes or ketones

• propargylamines by nucleophilic addition. The synthesis of propargylamines by diastereoselective reductive amination requires alkynyl ketones, which are difficult to prepare and are unstable towards reductive conditions. In approach I, organometallic nucleophiles are added to N-sulfinyl propargylimines, derived

• side chains in α-position, which are analogous or similar to amino acid side chains. In general, various aldehydes are condensed with Ellman’s chiral sulfinamide. Diastereoselective re-face addition of (trimethylsilyl)ethynyllithium to the (S)-configured sulfinimines 5 gives the corresponding N

A mechanochemical approach to access the proline–proline diketopiperazine framework

• Nicolas Pétry,
• Hafid Benakki,
• Eric Clot,
• Pascal Retailleau,
• Farhate Guenoun,
• Fatima Asserar,
• Chakib Sekkat,
• Thomas-Xavier Métro,
• Jean Martinez and
• Frédéric Lamaty

Beilstein J. Org. Chem. 2017, 13, 2169–2178, doi:10.3762/bjoc.13.217

• proline derivatives. The diastereoselective cyclization, which was clearly supported by DFT calculations is noteworthy. Further developments and applications of these scaffolds are currently underway. Optimized geometries for the two conformers presenting interactions with either Ca (16a) or Cb (16b). H

Enzymatic separation of epimeric 4-C-hydroxymethylated furanosugars: Synthesis of bicyclic nucleosides

• Neha Rana,
• Manish Kumar,
• Vinod Khatri,
• Jyotirmoy Maity and
• Ashok K. Prasad

Beilstein J. Org. Chem. 2017, 13, 2078–2086, doi:10.3762/bjoc.13.205

• ), diisopropyl ether (DIPE), toluene and dioxane. We carried out all ten sets of reactions for diastereoselective acetylation of epimeric mixtures of ribo- and xylotrihydroxyfuranosides 3a,b by using vinyl acetate at 30, 35, 40 and 45 °C and at 250 rpm in an incubator shaker to evaluate the appropriate lipase

• their detailed crystallographic data have been deposited in the Cambridge Crystallographic Data Centre with CCDC No. 1533725, 1533768 and 1532373, respectively. Conclusion A highly efficient and diastereoselective catalyzed Novozyme®-435-catalyzed acetylation methodology has been developed for the

Chiral phase-transfer catalysis in the asymmetric α-heterofunctionalization of prochiral nucleophiles

• Johannes Schörgenhumer,
• Maximilian Tiffner and
• Mario Waser

Beilstein J. Org. Chem. 2017, 13, 1753–1769, doi:10.3762/bjoc.13.170

• phase-transfer catalysis for α-sulfenylation reactions date back almost 20 years, when Wladislaw and co-workers described the diastereoselective α-sulfenylation of chiral β-ketosulfoxides 29 in the presence of achiral and chiral PTCs (Scheme 14, upper reaction) [127][128][129]. In a detailed

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

• obtained according to literature procedures [133], thus setting the stereochemistry at C12. The five-step sequence from 20 to vinyl iodide 21 included a (poorly diastereoselective) epoxidation, epoxide opening with a propynyl anion and a hydrozirconation/iodination reaction to generate the vinyl iodide

• iodide 21. As illustrated in Scheme 2, the nine-step synthesis of the latter proceeded via key epoxide 30 and comprised a diastereoselective alkylation of diethyl (S)-malate according to Seebach and Wasmuth [136] to introduce the C12-methyl group (dr = 8:1). Although being longer than the 1st generation

Effect of uridine protecting groups on the diastereoselectivity of uridine-derived aldehyde 5’-alkynylation

• Raja Ben Othman,
• Mickaël J. Fer,
• Laurent Le Corre,
• Sandrine Calvet-Vitale and
• Christine Gravier-Pelletier

Beilstein J. Org. Chem. 2017, 13, 1533–1541, doi:10.3762/bjoc.13.153

• modest diastereoselectivities (65:35) in favor of the 5’R-isomer, whereas O-silyl groups promoted higher diastereoselectivities (up to 99:1) in favor of the 5’S-isomer. A study related to this protecting group effect on the diastereoselectivity is reported. Keywords: diastereoselective alkynylation

• diastereoselective addition of a nucleophile on a carbonyl group. The latter can involve either the reduction of a ketone at C-5’ [12][33][34][35], or the addition on an aldehyde of various nucleophiles such as enolates [15][36][37][38], allylborane [39], dialkyl phosphites [40], TMSCN [41] or Grignard reagents [12

• ratio (Table 2, entry 15). The three attempts of C-5’ alkynylation of N-3-allylated uridine aldehydes, did not revealed marked influence on the diastereoselective ratio (Table 2, entries 3, 8, 15). To explain the diastereoselective outcome of the reaction, we first considered Cram chelated models

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

• isolate several exclusively β-glycosyl sulfonohydrazide (GSH) donors in very high yields (Figure 6) [92][93]. Furthermore, both C2–OH and 2-deoxy-2-NHAc saccharides were compatible with their conditions. Their initial study [92] focused on the diastereoselective glycosylation of 2-deoxy-2-NHAc sugars

Total syntheses of the archazolids: an emerging class of novel anticancer drugs

• Stephan Scheeff and
• Dirk Menche

Beilstein J. Org. Chem. 2017, 13, 1085–1098, doi:10.3762/bjoc.13.108

• Scheme 9. After reduction the alcohol was protected with TIPS and the TBS ether was cleaved by acetic acid to get to the primary alcohol 43. The reduction with (S)-alpine borane was highly diastereoselective (dr > 20:1). Following this sequence over 6 steps the two stereogenic centers at C7 and C8 were