1056028-66-0Relevant articles and documents
Functionalized aryl-β-C-glycoside synthesis by Barbier-type reaction using 2,4,6-triisopropylphenyllithium
Ohba, Kiyomi,Koga, Yuichi,Nomura, Sumihiro,Nakata, Masaya
, p. 1007 - 1010 (2015)
We developed an efficient synthetic route for functionalized aryl-β-C-glycosides, which are difficult to prepare by conventional methods. An aryl halide having an ester, cyano, or carbonyl group was treated with 2,4,6-triisopropylphenyllithium in the pres
A Salmochelin S4-Inspired Ciprofloxacin Trojan Horse Conjugate
Black, Conor M.,Boros, Eszter,Duhme-Klair, Anne-Kathrin,Herman, Reyme,Pandey, Apurva,Routledge, Anne,Sanderson, Thomas J.,Southwell, James W.,Thomas, Gavin H.,Wilde, Ellis J.
, p. 2532 - 2541 (2020/10/18)
A novel ciprofloxacin-siderophore Trojan Horse antimicrobial was prepared by incorporating key design features of salmochelin, a stealth siderophore that evades mammalian siderocalin capture via its glycosylated catechol units. Assessment of the antimicro
Mimicking salmochelin S1 and the interactions of its Fe(III) complex with periplasmic iron siderophore binding proteins CeuE and VctP
Wilde, Ellis J.,Blagova, Elena V.,Sanderson, Thomas J.,Raines, Daniel J.,Thomas, Ross P.,Routledge, Anne,Duhme-Klair, Anne-Kathrin,Wilson, Keith S.
, p. 75 - 84 (2018/10/31)
A mimic of the tetradentate stealth siderophore salmochelin S1, was synthesised, characterised and shown to form Fe(III) complexes with ligand-to-metal ratios of 1:1 and 3:2. Circular dichroism spectroscopy confirmed that the periplasmic binding proteins
Glycosyl Cross-Coupling of Anomeric Nucleophiles: Scope, Mechanism, and Applications in the Synthesis of Aryl C-Glycosides
Zhu, Feng,Rodriguez, Jacob,Yang, Tianyi,Kevlishvili, Ilia,Miller, Eric,Yi, Duk,O'Neill, Sloane,Rourke, Michael J.,Liu, Peng,Walczak, Maciej A.
supporting information, p. 17908 - 17922 (2017/12/26)
Stereoselective manipulations at the C1 anomeric position of saccharides are one of the central goals of preparative carbohydrate chemistry. Historically, the majority of reactions forming a bond with anomeric carbon has focused on reactions of nucleophiles with saccharide donors equipped with a leaving group. Here, we describe a novel approach to stereoselective synthesis of C-aryl glycosides capitalizing on the highly stereospecific reaction of anomeric nucleophiles. First, methods for the preparation of anomeric stannanes have been developed and optimized to afford both anomers of common saccharides in high anomeric selectivities. We established that oligosaccharide stannanes could be prepared from monosaccharide stannanes via O-glycosylation with Schmidt-type donors, glycal epoxides, or under dehydrative conditions with C1 alcohols. Second, we identified a general set of catalytic conditions with Pd2(dba)3 (2.5 mol%) and a bulky ligand (JackiePhos, 10 mol%) controlling the β-elimination pathway. We demonstrated that the glycosyl cross-coupling resulted in consistently high anomeric selectivities for both anomers with mono- and oligosaccharides, deoxysugars, saccharides with free hydroxyl groups, pyranose, and furanose substrates. The versatility of the glycosyl cross-coupling reaction was probed in the total synthesis of salmochelins (siderophores) and commercial anti-diabetic drugs (gliflozins). Combined experimental and computational studies revealed that the β-elimination pathway is suppressed for biphenyl-type ligands due to the shielding of Pd(II) by sterically demanding JackiePhos, whereas smaller ligands, which allow for the formation of a Pd-F complex, predominantly result in a glycal product. Similar steric effects account for the diminished rates of cross-couplings of 1,2-cis C1-stannanes with aryl halides. DFT calculations also revealed that the transmetalation occurs via a cyclic transition state with retention of configuration at the anomeric position. Taken together, facile access to both anomers of various glycoside nucleophiles, a broad reaction scope, and uniformly high transfer of anomeric configuration make the glycosyl cross-coupling reaction a practical tool for the synthesis of bioactive natural products, drug candidates, allowing for late-stage glycodiversification studies with small molecules and biologics.
Diastereoselective Ni-catalyzed Negishi cross-coupling approach to saturated, fully oxygenated C-alkyl and C-aryl glycosides
Gong, Hegui,Gagne, Michel R.
supporting information; experimental part, p. 12177 - 12183 (2009/02/05)
A Ni-catalyzed Negishi cross-coupling approach to C-glycosides is described with an emphasis on C-aryl glycosides. The combination of NiCl 2/PyBox in N,N′-dimethylimidazolidinone (DMI) enabled the synthesis of C-alkyl glycosides under mild reaction conditions. Moderate yields and β-selectivities were obtained for C-glucosides, and good yields and high α-selectivities were the norm for C-mannosides. For C-aryl glycosides, reactions employing Ni(COD)2/tBu-Terpy in N,N-dimethylformamide (DMF) were typically high yielding and provided C-glucosides with high β-selectivities (1:>10 α:β) and C-mannosides in moderate α-selectivities (3:1 α:β); α-C-aryl glycosides could be obtained by the combination of Ni(COD) 2/PyBox in DMF (>20:1 α:β). The collective studies suggest that stereochemical control of the C-glycosides is dependent on the substrate and catalysts combination. The Negishi protocol displays excellent functional group tolerance, as demonstrated by its use in the first total synthesis of the natural product salmochelin SX.
