Rhodium(III)-Catalyzed Cascade [5 + 1] Annulation/5-exo-Cyclization Initiated by C-H Activation: 1,6-Diynes as One-Carbon Reaction Partners

Organic Letters
Fen XuMiao Du

Abstract

The catalytic [5 + 1] annulation/5-exo-cyclization reaction of amidines with diynes is reported herein. This protocol provides highly atom-economical access to fabricate two nitrogen-containing heterocycles in one step with high efficiency and selectivity. Significantly, this reaction represents the first example of using diyne as a one-carbon reaction partner in C-H functionalization. Kinetic isotope effects suggested that the catalytic cycle of this reaction is initiated by the cleavage of the ortho C-H bond in the N-phenyl ring of amidines, which is likely involved in the rate-limiting step. Calculations based on density functional theory (DFT) indicated that C-H activation and the formation of Rh(V) species via 5-exo-cyclization could be vital processes for this cascade transformation.

References

Sep 11, 2003·Chemical Reviews·Jesús A Varela, Carlos Saá
Jan 30, 2008·Angewandte Chemie·Gordon Brasche, Stephen L Buchwald
Jul 29, 2010·Journal of the American Chemical Society·Todd K Hyster, Tomislav Rovis
Mar 11, 2011·Chemical Society Reviews·Lindsay McMurrayMatthew J Gaunt
Mar 18, 2011·Angewandte Chemie·Timothy Newhouse, Phil S Baran
Apr 2, 2011·Journal of the American Chemical Society·Nicolas GuimondKeith Fagnou
Nov 25, 2011·Journal of the American Chemical Society·Philipp KoschkerBernhard Breit
Mar 2, 2012·Chemical Society Reviews·Guoyong SongXingwei Li
Dec 19, 2012·Journal of the American Chemical Society·Jamie M Neely, Tomislav Rovis
Oct 23, 2014·Journal of the American Chemical Society·Yuki FukuiGuo-Qiang Lin
Dec 23, 2014·Chemical Reviews·Xun-Xiang GuoWanbin Zhang
Mar 11, 2015·Accounts of Chemical Research·Olafs DaugulisLy Dieu Tran
Jul 22, 2015·Journal of the American Chemical Society·Sharon R NeufeldtK N Houk
Mar 19, 2016·Chemistry : a European Journal·Ruhuai MeiLutz Ackermann
Apr 14, 2016·Chemical Society Reviews·T GenschJ Wencel-Delord
Jun 23, 2016·Angewandte Chemie·Moisés Gulías, José Luis Mascareñas
Jul 14, 2016·Angewandte Chemie·Alexander P Pulis, David J Procter
Jul 22, 2016·Nature Chemistry·Christopher D RolandAdam S Veige
Aug 2, 2016·Angewandte Chemie·Ru-Yi ZhuJin-Quan Yu
Jan 19, 2017·Journal of the American Chemical Society·Cheng-Qiang WangTeck-Peng Loh
Apr 5, 2017·Accounts of Chemical Research·Olivier Baudoin
Apr 8, 2017·Journal of the American Chemical Society·Yan XuGuangbin Dong
Apr 19, 2017·Journal of the American Chemical Society·Xiaoming WangFrank Glorius
May 14, 2017·Angewandte Chemie·Huai-Wei WangJin-Quan Yu
May 26, 2017·Chemical Society Reviews·Lucy PingSang-Gi Lee

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