Synthesis of Unsymmetrical 1,3-Diynes via Pd/Cu-Catalyzed Cross-Coupling of Terminal Alkynes at Room Temperature

A facile and practical synthetic route of unsymmetrical 1,3-diynes via the PdC1/CuI catalyzed oxidative coupling of two different terminal alkynes has been developed by using 3-（diphenylphosphino）propanoic acid as a ligand in the presence of oxygen. This system is suitable for not only aromatic alkynes but also heteroaromatic and aliphatic alkynes which were transformed into the corresponding unsymmetrical 1,3-diynes in moderate to good yields at room temperature. Moreover, the unsymmetrical 1,3-diynes were also obtained on a multi-gram scale. Mechanistic studies suggest that oxygen plays a key role in the catalytic cycles.

Ligand-Free Synthesis of 1,4-Disubstituted-l,3-diynes by Iron/Copper Cocatalyzed Homocoupling of Terminal Alkynes

A simple and efficient protocol for Fe/Cu cocatalyzed oxidative homocoupling reaction of terminal alkynes to symmetrical 1,4-disubstituted-l,3-diynes was presented. The results showed that both CuBr and FeC13 played erucial roles in the reaction. It is noteworthy that this protocol employs mild, efficient, aerobic and ligand free conditions. The alkynes, including aromatic, heteroaromatic and aliphatic alkynes, were transformed into the corresponding 1,3-diynes in good to excellent yields.

Catalytic Enantioselective 1,2-Addition of Terminal 1,3-Diynes to Trifluoromethyl Ketones

A facile catalytic enantioselective 1,2-addition of diynes to trifluoromethyl ketones was developed. By a com- bination of Me2Zn, Ti（OPr-i）4, BaF2 and quinine, the reaction of a series of terminal diynes with trifluoromethyl ke- tones proceeded to afford trifluoromethylated chrial tertiary alcohols with the diyne moiety in good to high yields with moderate to high enantioselectivities. Furthermore, this catalytic asymmetric diyne addition to trifluoro- methylketone was applied in the synthesis of the Efavirenz analogue.

膦酰保护基促进选择性Hay偶联制备非对称1,3-二炔（英文）

报道了芳香末端炔烃与单膦酰基-保护二炔的选择性Hay偶联反应. Ph_2P(O)的极性使得产物非对称1,3-二炔易与副产物分离.单膦酰基-保护二炔的低反应活性减少了自身氧化偶联,从而提高了目标产物的产率.很多芳香末端炔烃与单膦酰基-保护二炔都能应用于本Hay偶联反应,且相应非对称1,3-二炔产物的产率为中等到好.产物非对称1,3-二炔能用于合成非对称炔-二炔烃及环多炔烃.

A Facile Synthetic Route to New Fluorinated Building-Blocks of 1-Fluoroalkynes and 1-Fluorodiynest

A facile and direct fluorination process of alkynes and diynes was developed, in the presence of n-butyllithium, the reaction of a series of terminal alkynes and diynes with the electrophilic fluorinating reagent （NFSI） proceeded to afford various 1-fluoroalkynes and 1-fluoro-l,3-diynes in moderate to high yields.

Glaser Coupling Reaction without Organic Solvents and Bases under Near-critical Water Conditions

A Glaser coupling reaction of terminal alkynes in the presence of cupric chloride without organic solvents and bases under near-critical water has been developed.

Revealing efficient catalytic performance of N-CuO_(x) for aerobic oxidative coupling of aliphatic alkynes:A Langmuir-Hinshelwood reaction mechanism

O_(x)idative couplings of aliphatic alkynes are crucial for the production of naturally occurring 1,3-diynes.Herein we report the novel approach for effective synthesis of unsaturated coordinated N doped copper oxides(N-CuO_(x))catalyst,and uncover that N-CuO_(x) catalyst as an additive-free and cost-effective heterogeneous catalyst has highly catalytic performance for directly oxidative coupling of aliphatic alkynes.The key to achieve efficient oxidative coupling of aliphatic alkynes is the synergistic effect of N species and uncoordinated O/Cu species caused by N dopants,which undergoes the Langmuir–Hinshelwood reaction mechanism.The N-CuO_(x) catalyst displays~89.1%yield for hexadeca-7,9-diyne under mild conditions and stable reusability(5 cycles),showing significant advances compared with the traditionally copper oxides.These findings highlight the heteroatom dopants that provide a new methodology for designing efficient copper catalysts in synthesis of naturally occurring 1,3-diynes.