Synthesis of 6-Selanyl-2-triazolylpurine Derivatives Using 2,6-Bistriazolylpurines as Starting Materials.

Two pathways toward 6-selanyl-2-triazolylpurine derivatives were designed. The first method involved the synthesis of 2-chloro-6-selanylpurine derivatives, further SNAr reaction with NaN3, and following CuAAC using different alkynes. The second method was based on the synthesis of 2,6-bistriazolylpurine derivatives as starting materials followed by SNAr reaction with commercial or in situ generated selenols as nucleophiles. A series of 2-chloro-6-selanylpurine derivatives were obtained in yields up to 84%. It was found that in the latter compounds, 6-selanyl moiety was the better leaving group compared to 2-chlorosubstituent in SNAr reactions. On the other hand, the SNAr reaction between 2,6-bistriazolylpurines and selenols or diselenides was successful, and 13 examples of 6-selanyl-2-triazolylpurine derivatives were obtained in yields up to 87%. This direct approach for the Se-C bond formation proved the ability of the 1,2,3-triazolyl ring at the C6 position of purine to act as a good leaving group.

1,2-Silyl Shift-Induced Heterocyclization of Propargyl Silanes: Synthesis of Five-Membered Heterocycles Containing a Functionalized Olefin Side Chain.

Propargyl silanes with a terminal alkyne moiety undergo a 1,2-silyl shift when activated with electrophiles such as H+, Br+, I+, and PhSe+. A method was developed to trap 1,3-transposed electrophilic centers with various internal O-, N-, and S-nucleophiles in a 5-exo manner. This synthetic procedure provided five-membered heterocycles containing a trisubstituted olefin side chain. The scope of the method includes access to tetrahydrofuran, γ-butyrolactone, 2-isooxazoline, pyrrolidine, and thiolane derivatives in yields ranging from 25 to 85% (23 examples in total). Reactions with TsNBr2 ensured complete (E)-selectivity of the newly formed olefins. Further functionalization of the obtained 1-trialkylsilyl-2-bromovinyl side chain was demonstrated by double-bond geometry-preserving electrophilic substitution and cross-coupling reactions that provided heterocycles with a trisubstituted vinyl moiety.

Photophysical and Electrical Properties of Highly Luminescent 2/6-Triazolyl-Substituted Push-Pull Purines.

New push-pull N(9)-alkylated 6-piperidino-2-triazolylpurine and 2-piperidino-6-triazolylpurine derivatives are synthesized, and their optical and optoelectronic properties are comprehensively characterized with experimental and computational methods. The compounds possess intense violet or blue fluorescence with fluorescence quantum yields of up to 91% in solution and 40% in host-free films. Depending on their structural composition, the compounds have ionization energy in the range of 5.25-6.04 eV, electron affinity of 2.18-3.15 eV, and triplet energy of 2.52-2.95 eV. Due to the presence of hole-transporting purine and electron-transporting triazole fragments, compounds exhibit bipolar charge-transportation ability. Despite the favorable emissive properties of the studied push-pull purines, their electroluminescence in thin films is quenched owing to large current densities that are present even at a moderate driving voltage. This marks application directions related to a predominantly charge-transportation functionality as the most suitable for this compound class.

Synthesis of Sulfones via Ru(II)-Catalyzed Sulfination of Boronic Acids.

Ruthenium(II) complexes catalyze the insertion of sulfur dioxide into (het)aryl and alkenyl boronic acids. The transmetalation-sulfination process proceeds with DABSO in the presence of 5 mol % RuCl2(PPh3)3 in methanol at 100 °C. The intermediate sulfinate salt can be quenched with various electrophiles such as alkyl halides, epoxides, Michael acceptors, and λ3-iodanes in moderate to good yields. The reported sulfone synthesis can be performed either as a direct one-pot or one-pot two-step procedure depending on the reactivity of the electrophile.

Brønsted Acid Catalyzed 1,2-Silyl Shift in Propargyl Silanes: Synthesis of Silyl Dienes and Silyl Indenes.

A general method for generation of allyl carbenium ions from propargyl silanes via a 1,2-silyl shift by Brønsted acids is reported. Two possible reaction pathways are described. Deprotonation results in silyl dienes with yields from 52% to 92%. Intramolecular Friedel-Crafts reactions of aryl-substituted systems give access to silyl indenes with yields of 18-90% depending on the substitution pattern. The obtained products have been shown to react as alkenyl silanes in Hiyama coupling and electrophilic substitution and as dienes in Diels-Alder cycloaddition.

In(III) and Hf(IV) Triflate-Catalyzed Hydration and Catalyst-free Hydrohalogenation of Aryl Acetylenes in Liquid Sulfur Dioxide.

The use of liquid sulfur dioxide as a reaction solvent to promote chemical transformations of alkynes has been explored. First, a combination of liquid SO2 and In(OTf)3 or Hf(OTf)4 as a catalyst allows to perform hydration of aryl alkynes under mild conditions without a direct addition of Brønsted acid. Second, novel catalyst-free conditions for the synthesis of α-vinyl iodides, bromides, and chlorides from aryl alkynes have been developed in liquid SO2 using group I and II metal halides and ammonium iodide as the halide ion sources.