Synergy of activating substrate and introducing CH··· O interaction to achieve Rh 2 (II)-catalyzed asymmetric cycloisomerization of 1, n-enynes

Release time:2021-07-02

DOI number:10.1007/s11426-020-9794-3

Abstract:We report the first Rh2(II)-catalyzed asymmetric cycloisomerization of activated enynes to provide cyclopropane-fused tetra-hydropyridines in good yields and excellent enantioselectivities under mild conditions. The activated group, CHZ (Z is electron-withdrawing group (EWG)), in the enyne substrates exerts two synergetic roles, one is to activate alkyne for the cyclopropanation reaction; the other is to introduce the C-H···O interaction between substrate and catalyst (reducing the energy barrier of the reaction). This double-mode activation was supported by both density functional theory (DFT) calculations and experimental tests. This strategy was also extended to other CH2Z (Z can be OH, OMe, F) as activating groups that made the CH2 more acidic so that the substrates could also form increased C-H···O interaction with the catalyst.

First Author:Rui Wu#, Kai Chen#, Jun Ma#

Indexed by:Journal paper

Correspondence Author:Zhi-Xiang Yu*, Shifa Zhu*

Discipline:Natural Science

First-Level Discipline:Chemistry

Document Type:J

Volume:63

Issue:9

Page Number:1230-1239

Translation or Not:no

Date of Publication:2020-09-01

Included Journals:SCI

Links to published journals:https://link.springer.com/article/10.1007/s11426-020-9794-3