Organic & Biomolecular Chemistry最新文献

A direct and convenient strategy for the assembly of indolo[1,2-f]phenanthridine via a Pd-catalyzed tandem cyclization reaction is presented. The current strategy delivers a range of indolo[1,2-f]phenanthridine derivatives by utilizing readily available 1-(2-iodophenyl)-1H-indole and commercially available o-bromobenzoic acids as the starting materials. The reaction features the formation of two C-C bonds through Pd-catalyzed C-H bond activation and decarboxylation.

While Mn²⁺ ions are well-established for reducing the fidelity of DNA polymerases, leading to the misincorporation of nucleotides, our investigation of the effects of metal ions revealed a contrasting role of Zn²⁺. Here, we demonstrate that Zn²⁺ ions enhance the fidelity of DNA polymerases (the 3' → 5' exonuclease-deficient Klenow fragment and Taq DNA polymerase) by suppressing misincorporation during primer extension reactions. Remarkably, Zn²⁺ ions inhibit both intrinsic misincorporation and Mn²⁺-induced misincorporation of nucleotides. Furthermore, Zn²⁺ ions also effectively suppressed misincorporation during metal-mediated primer extension reactions, which involved forming Ag⁺ and Hg²⁺ ion-mediated base pairs. These findings suggest that Zn²⁺ ions inhibit both intrinsic and Mn²⁺-induced mismatched base pair formation. Consequently, the combined use of Mn²⁺ and Zn²⁺ ions may offer a strategy for precisely regulating the fidelity of DNA polymerases. Remarkably, Zn²⁺ ions even suppress misincorporation in primer extension reactions that rely on metal-mediated base pairs, and conversely, this suggests that DNA polymerases recognize metal-mediated base pairs such as T-Hg²⁺-T, C-Ag⁺-A, and C-Ag⁺-T as relatively stable base pairs. These results imply that Zn²⁺ ions may also enhance the fidelity of DNA polymerases when incorporating non-canonical nucleobases, potentially paving the way for the expansion of the genetic alphabet.

In this study, we present our preliminary findings on the synthesis of carbazole derivatives involving the Sonogashira coupling reaction of 2-(trimethylamino)methylindolyltriflates with aryl acetylenes followed by isomerization, thermal electrocyclization and 1,3-H shift, furnishing the respective di- and tri-substituted carbazoles.

A highly efficient methodology has been developed for the synthesis of 1,4-benzodioxepines through electrochemical oxyselenenylation of 2-O-tethered alkenyl phenylmethanol and diselenides under external oxidant-free conditions at room temperature. Experimental evidence supports this transformation to occur via a radical mechanism.

A simple mono/dialkylation of acrylamide derivatives was achieved, affording diverse mono/dialkylated benzo[4,5]imidazo[2,1-a]isoquinolines or polycyclic coumarins with good substrate scope. This system used common peroxides as alkylating reagents. Meanwhile, a series of scaled-up reactions and mechanistic explorations well demonstrated the application and reaction process of this cascade system.

We herein describe an alkylation reaction of indoles with NHC salts to access bis(indolyl)methanes as product. The NHC salt (or free NHC) serves as a C1 precursor due to decomposition of its N-heterocyclic ring. Although the exact roles of zinc powder and acetic/formic acid remain elusive, both of them are indispensable for this reaction. Two possible reaction pathways are proposed based on the results of mechanistic experiments.

A preparative synthesis of previously unknown 21- and 14-membered azamacrocycles via acid-promoted cyclotrimerization or cyclodimerization of three readily available precursors, namely, 1-amino-6-hydroxy-4,6-dimethylhexahydropyrimidine-2-thione, 4-(4-oxopent-2-yl)thiosemicarbazide hydrazone, and 5,7-dimethyl-1,4,5,6-tetrahydro-3H-1,2,4-triazepine-3-thione has been developed. A dramatic dependence of the selectivity of macrocyclization on the reaction conditions is demonstrated. The thermodynamic aspects of the reactions are discussed based on experimental data and DFT calculation results. Plausible pathways for the formation of macrocycles are proposed.

This investigation presents the synthesis of butyl-decorated calix[n]phenoxazines of varying sizes by kinetic control and the ring-expansion of calix[3]phenoxazine, which uniquely exhibits distinct binding affinities for fullerenes C₆₀ and C₇₀. Calix[3]phenoxazine demonstrates a higher binding affinity for cationic ammonium, which can be reversibly deprotonated and protonated, enabling the reversible release and reloading of fullerenes. This system holds potential for applications in fullerene extraction and separation.

We described a chiral phosphoric acid (CPA) catalyzed asymmetric [3 + 3] cycloaddition of cinnamaldehyde-derived N-aryl nitrones with 2-indolylmethanols to prepare various indole-fused 1,2-oxazines in high yields (up to 96%) with excellent enantioselectivity (>99% ee). Control experiments indicate that hydrogen bonding plays important roles in controlling the enantioselectivity of products. This strategy provides an efficient pathway to construct enantioenriched indole-fused 1,2-oxazines from N-aryl nitrones with 2-indolylmethanols.

Carbon-halogen bond cleavage in aryl halides through single electron transfer (SET) is a crucial step in radical-based cross-coupling reactions. Accomplishing such cleavage using an organic system without the assistance of any transition metal-based catalyst is highly challenging. In recent years, combining organic molecules and a base has served as a unique system for SET-mediated carbon-halogen bond cleavage. Herein, we report the combination of simple benzylamine and potassium tert-butoxide as a super-electron-donor system for SET-mediated cleavage of aryl halides generating reactive aryl radicals, which subsequently react with arenes or heteroarenes and produce biaryl skeletons. The new methodology enables the arylation of arenes and heteroarenes with aryl iodides, or aryl bromides, upon excitation with heat or light. The broad substrate scope, mild reaction conditions and tolerance of common organic functional groups offer an efficient alternative route for direct C-H arylation reactions.