TY - JOUR
T1 - Skeletal rearrangement of O-propargylic formaldoximes by a gold-catalyzed cyclization/intermolecular methylene transfer sequence
AU - Nakamura, Itaru
AU - Gima, Shinya
AU - Kudo, Yu
AU - Terada, Masahiro
PY - 2015/6/1
Y1 - 2015/6/1
N2 - Abstract Skeletal rearrangement of O-propargylic formaldoximes, in the presence of gold catalysts, afforded 4-methylene-2-isoxazolines in good to excellent yields by an intermolecular methylene transfer. In addition, the cascade reaction with maleimide in the presence of a gold catalyst afforded isoxazole derivatives by cyclization/methylene transfer and a subsequent ene reaction, whereas that using a copper catalyst gave oxazepines through a 2,3-rearrangement. Au is not like Cu: Skeletal rearrangement of O-propargylic formaldoximes, in the presence of gold catalysts effectively afforded 4-methylene-2-isoxazolines by intermolecular methylene transfer. The cascade reaction in the presence of gold proceeds by cyclization/methylene transfer and a subsequent ene reaction, whereas with a copper catalyst it proceeds by a 2,3-rearrangement.
AB - Abstract Skeletal rearrangement of O-propargylic formaldoximes, in the presence of gold catalysts, afforded 4-methylene-2-isoxazolines in good to excellent yields by an intermolecular methylene transfer. In addition, the cascade reaction with maleimide in the presence of a gold catalyst afforded isoxazole derivatives by cyclization/methylene transfer and a subsequent ene reaction, whereas that using a copper catalyst gave oxazepines through a 2,3-rearrangement. Au is not like Cu: Skeletal rearrangement of O-propargylic formaldoximes, in the presence of gold catalysts effectively afforded 4-methylene-2-isoxazolines by intermolecular methylene transfer. The cascade reaction in the presence of gold proceeds by cyclization/methylene transfer and a subsequent ene reaction, whereas with a copper catalyst it proceeds by a 2,3-rearrangement.
KW - copper
KW - gold
KW - heterocycles
KW - rearrangements
KW - synthetic methods
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U2 - 10.1002/anie.201501856
DO - 10.1002/anie.201501856
M3 - Article
AN - SCOPUS:85027946411
VL - 54
SP - 7154
EP - 7157
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
SN - 1433-7851
IS - 24
ER -