Recently, Angewandte Chemie International Edition, a top chemistry journal, published a paper contributed in part by Prof. Zhang Xumu and Assoc. Prof. Dang Li of Chemistry at SUSTech, developing the first rhodium(I)-catalyzed asymmetric cycloisomerization of (E)-1,6-enyesthat afford highly functionalized five-membered cycles.

 Prof. Zhang Xumu

Assoc. Prof. Dang Li 

In order to obtain useful medicine precursors, an enantioselective rhodium(I)-catalyzed cycloisomerization reaction of challenging (E)-1,6-enynes was developed by Prof. Zhang Xumu and the reaction mechanism for the enantioselectivity was investigated by Dr. Dang Li . This novel process enables (E)-configured-1,6-enynes with wide range of functionalities, which include nitrogen, oxygen, carbon-tethered (E)-configured-1,6-enynes, to undergo the cycloisomerization with excellent enantioselectivity, in a high-yielding and operationally simple manner.

This new process features not only high enantiomeric excess (>99 % ee), but also broad substrate scope and functionality tolerance, wherein both terminal and internal alkynes with a variety of functional groups are tolerated, which provides a complementary approach for undertaking rhodium(I)-catalyzed cycloisomerization of 1,6-enynes. Moreover, this RhI-diphosphane catalytic system also exhibited superior reactivity and enantioselectivity for (Z)-1,6-enynes. Finally, a DFT study provides the necessary insight to understand the reactivity difference between RhI-TangPhos and RhI-BINAP for cycloisomerization of 1,6-enynes. We anticipate that this process will find significant utility in target directed synthesis given the ubiquity of (E)-configured olefins.

Click on the link below to see the original article：

http://onlinelibrary.wiley.com/doi/10.1002/anie.201601061/full