TY - JOUR
T1 - Transition-metal-free direct arylation
T2 - Synthesis of halogenated 2-amino-2′-hydroxy-1,1′-biaryls and mechanism by DFT calculations
AU - Gao, Hongyin
AU - Ess, Daniel H.
AU - Yousufuddin, Muhammed
AU - Kürti, László
PY - 2013/5/15
Y1 - 2013/5/15
N2 - A transition-metal-free, regioselective direct aryl-aryl bond-forming process for the synthesis of halogenated 2-amino-2′-hydroxy-1,1′- biaryls that are currently either inaccessible or challenging to prepare using conventional methods is disclosed. The addition of ArMgX to an o-halonitrobenzene at low temperature generates a transient N,O- biarylhydroxylamine that rapidly undergoes either [3,3]- or [5,5]-sigmatropic rearrangement in one-pot to form a 2-amino-2′-hydroxy-1,1′-biaryl or 1-amino-1′-hydroxy-4,4′-biaryl, respectively. The periselectivity is controlled by the choice of solvent and temperature. This direct arylation process is also readily scalable (1-10 mmol). DFT calculations suggest that from the N,O-biarylhydroxylamine intermediate there is a low-energy stepwise pathway that involves initial Mg-mediated N-O bond cleavage followed by pathway branching toward either [3,3]- or [5,5]-rearrangement products via C-C bond formation and rearomatization.
AB - A transition-metal-free, regioselective direct aryl-aryl bond-forming process for the synthesis of halogenated 2-amino-2′-hydroxy-1,1′- biaryls that are currently either inaccessible or challenging to prepare using conventional methods is disclosed. The addition of ArMgX to an o-halonitrobenzene at low temperature generates a transient N,O- biarylhydroxylamine that rapidly undergoes either [3,3]- or [5,5]-sigmatropic rearrangement in one-pot to form a 2-amino-2′-hydroxy-1,1′-biaryl or 1-amino-1′-hydroxy-4,4′-biaryl, respectively. The periselectivity is controlled by the choice of solvent and temperature. This direct arylation process is also readily scalable (1-10 mmol). DFT calculations suggest that from the N,O-biarylhydroxylamine intermediate there is a low-energy stepwise pathway that involves initial Mg-mediated N-O bond cleavage followed by pathway branching toward either [3,3]- or [5,5]-rearrangement products via C-C bond formation and rearomatization.
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U2 - 10.1021/ja400897u
DO - 10.1021/ja400897u
M3 - Article
C2 - 23470200
AN - SCOPUS:84877799209
SN - 0002-7863
VL - 135
SP - 7086
EP - 7089
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 19
ER -