有机张力分子弯键特征的理论研究

提出了任意张力分子中弯键特征的计算公式，对一系列典型的有机张力分子──单环烃、双环烃、螺桨烷、多面体烷及部分不饱和环状烃的结构、张力、稳定性及反应性之间的关系进行了研究，其弯键特征的理论研究表明：有机张力分子的Ｃ－Ｃ键均发生不同程度弯曲，且Ｃ－Ｃ弯键之间的夹角与四面体杂化角度１０９．５°的差值△β可成为有机分子张力与稳定性的量度。

Changing the balance of the MTO reaction dual-cycle mechanism: Reactions over ZSM-5 with varying contact times

The methanol to olefins （MTO） reaction was performed over ZSM‐5 zeolite at 300℃ under various methanol weight hourly space velocity （WHSV） values. During these trials, the catalytic perfor‐mance was assessed, in addition to the formation and function of organic compounds retained in the zeolite. Analysis of reaction effluents and confined organics demonstrated a dual‐cycle reaction mechanism when employing ZSM‐5. The extent of the hydrogen transfer reaction, a secondary reac‐tion in the MTO process, varied as the catalyst‐methanol contact time was changed. In addition, 12C/13C‐methanol switch experiments indicated a relationship between the dual‐cycle mechanism and the extent of the hydrogen transfer reaction. Reactions employing a low methanol WHSV in conjunction with a long contact time favored the hydrogen transfer reaction to give alkene products and promoted the generation and accumulation of retained organic species, such as aromatics and methylcyclopentadienes, which enhance the aromatic cycle. When using higher WHSV values, the reduced contact times lessened the extent of the hydrogen transfer reaction and limited the genera‐tion of methylcyclopentadienes and aromatic species. This suppressed the aromatic cycle, such that the alkene cycle became the dominant route during the MTO reaction.

Enantioselective epoxidation of olefins with hydrogen peroxide catalyzed by bioinspired aminopyridine manganese complexes derived from L-proline

Three chiral aminopyridine ligands derived from L-proline were prepared. Careful evaluation of the corresponding aminopyridine manganese complexes in asymmetric epoxidation of olefins revealed a broad substrate scope in the presence of 0.2 mol% manganese complex and 0.5 equiv. 2,2-dimethylbutyric acid, with aqueous hydrogen peroxide as an oxidant. A variety of olefins including styrenes, chromenes, and cinnamamides were transformed successfully into the target epoxides with moderate to excellent enantioselectivity（yield up to 95%, ee up to 99%）.

Visible light promoted difunctionalization reactions of alkynes

Visible light promoted difunctionalization of alkynes is reviewed. The difunctionalization reaction is achieved by different reagents. Radicals such as carbon(sp3), carbon(sp2), and other heteroatom(P, S, N, Se, O, and halide) radicals initiated by visible light can undergo radical addition to a carbon-carbon triple bond. Upon further transformation, the desired difunctionalized products are obtained. Some organometallic complexes can be activated by visible light;the difunctionalization of alkynes is catalyzed by these species. Other reagents like 1,3-dipole precursors could also react with alkynes to give difunctionalization products;here, the 1,3-dipole derivatives are obtained by visible light photocatalysis. So far, the strategy has been succeeded in the formation of C–C bonds and C–X bonds. Several valuable chemical skeletons have been constructed under mild conditions. However, high regio-and stereoselectivities in some direct difunctionalization methodologies are yet to be achieved.