Cationic P(OPh)3- or PPh3-rhodium(I) complex-catalyzed isomerizations of 5-alkynals to ﾎｴ-alkynyl ketones, cyclopent-1-enyl ketones, and cyclohexenones.
英文:
Cationic P(OPh)3- or PPh3-rhodium(I) complex-catalyzed isomerizations of 5-alkynals to ﾎｴ-alkynyl ketones, cyclopent-1-enyl ketones, and cyclohexenones.
著者
和文:
Ken Tanaka,
Kaori Sasaki,
Kenzo Takeishe,
Masao. Hirano.
英文:
Ken Tanaka,
Kaori Sasaki,
Kenzo Takeishe,
Masao. Hirano.
A catalytic isomerizations of 5-alkynals to ﾎｳ-alkynyl ketones and cyclopent-1-enyl ketones using [Rh{P(OPh)3}2]BF4 as a catalyst has been developed. Cu(OTf)2 and AgBF4 are also effective catalysts for the formation of ﾎｳ-alkynyl ketones. The substituents at the 4-positions in 5-alkynals play important roles in the selection of two different isomerization pathways. The first catalytic endo/trans hydroacylation of acyclic 5-alkynals leading to cyclohexenones was also developed with [Rh(PPh3)2]BF4 as a catalyst. Crossover deuterium-labeling studies indicated that these isomerization reactions proceed intramolecularly. [on SciFinder(R)]
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