Directed Cleavage of Unstrained  Carbon‐Carbon Bond Penghao Chen Dongg Groupp Seminar November, 5th, 2014 Time‐line of Directing Moieties NN M O N M N N N M 1999‐2010 M M O O O 1984‐2003 2009‐2012 11998811‐11998866 22000055‐22001111 O N 11998800 11998888 11999966 22000044 [P] 22001122 OO MM M [P] O Suggs Ruhland Jun (8‐acylquinolines) Oshima MMuraii DDougllas, JJohhnson, WWang Jun (2‐amino‐3‐picoline) Shi 8‐Acylquinolines 8‐Acylquinolines 100mol%Rh(PPh ) Cl N 3 3 L DCM,40oC,10min Cl Rh O L O R R L 100mol%anhydrousHCl R=tBu Cl Rh DCM,35oC,20min R R=Ph L O R 100mol%Rh(PPh ) Cl N 3 3 N.R. DCM,40oC,10min Ph O J.WilliamsSuggs,ShermanD.Cox,J.Organomet.Chem.1981,122,199 8‐Acylquinolines R=benzyl 110000mmooll%%[[RRhhCCll((=)) ]] N 2222 N EEtt benzene,R.T. Me Cl Rh R O R O -C2Ph -CD Ph wilkinson'sgaveN.R. 2 insolublepolymer Py N PMe3/PPh3/CO N Cl Rh R O R O PPyy Br 2 insolublepolymer RBr J.WilliamSuggs,Chul-HoJun,J.Am.Chem.Soc.1984,106,3054 8‐Acylquinolines 8‐Acylquinolines 8‐Acylquinolines Ashley M. Dreis, Christopher J. Douglas J. Am. Chem. Soc. 2009, 131, 412 8‐Acylquinolines 10 mol % hydroquinone added AshleyM.Dreis,ChristopherJ.DouglasJ.Am.Chem.Soc.2009,131,412 8‐Acylquinolines N OO OH Ashley M. Dreis, Christopher J. Douglas J. Am. Chem. Soc. 2009, 131, 412