TY - JOUR
T1 - Reaction of aminodihydropentalenes with HB(C6F5) 2
T2 - The crucial role of dihydrogen elimination
AU - Xu, Bao Hua
AU - Kehr, Gerald
AU - Fröhlich, Roland
AU - Grimme, Stefan
AU - Erker, Gerhard
PY - 2011/3/16
Y1 - 2011/3/16
N2 - The aminodihydropentalene derivative 1a reacts with the Lewis acidic RB(C6F5)2 boranes (2a-c) by C-C bond cleavage to yield the formal borylene insertion products 3. In contrast, 1a,b react with HB(C6F5)2 at 55 °C by elimination of dihydrogen to yield the iminium-stabilized zwitterionic heterofulvenes 10a,b. The reaction pathways were studied by preparation of the kinetically controlled intermediates 7a,b and the thermodynamically controlled products 9a,b, monitored by variable-temperature NMR experiments, and supported by DFT calculations. The trapping reactions of 9a with HCl and PhCHO, respectively, led to the addition products 13 and 14. Compounds 3c, 7a,b, 10a,b, 11, 13, and 14 were characterized by X-ray diffraction.
AB - The aminodihydropentalene derivative 1a reacts with the Lewis acidic RB(C6F5)2 boranes (2a-c) by C-C bond cleavage to yield the formal borylene insertion products 3. In contrast, 1a,b react with HB(C6F5)2 at 55 °C by elimination of dihydrogen to yield the iminium-stabilized zwitterionic heterofulvenes 10a,b. The reaction pathways were studied by preparation of the kinetically controlled intermediates 7a,b and the thermodynamically controlled products 9a,b, monitored by variable-temperature NMR experiments, and supported by DFT calculations. The trapping reactions of 9a with HCl and PhCHO, respectively, led to the addition products 13 and 14. Compounds 3c, 7a,b, 10a,b, 11, 13, and 14 were characterized by X-ray diffraction.
UR - https://www.scopus.com/pages/publications/79952601016
U2 - 10.1021/ja1092369
DO - 10.1021/ja1092369
M3 - Article
AN - SCOPUS:79952601016
SN - 0002-7863
VL - 133
SP - 3480
EP - 3491
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 10
ER -