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Reversing the Reactivity of Carbonyl Functions with Phosphonium Salts: Enantioselective Total Synthesis of (+)‐Centrolobine
Author(s) -
Fujioka Hiromichi,
Yahata Kenzo,
Kubo Ozora,
Sawama Yoshinari,
Hamada Tomohito,
Maegawa Tomohiro
Publication year - 2011
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201106046
Subject(s) - enantioselective synthesis , phosphonium , alkylation , trimethylsilyl , chemistry , reactivity (psychology) , yield (engineering) , total synthesis , organic chemistry , combinatorial chemistry , medicinal chemistry , catalysis , materials science , medicine , alternative medicine , pathology , metallurgy
Step saver : Carbonyl groups with lower reactivities can be transformed in the presence of more reactive ones by treatment with PPh 3 (or PEt 3 ) and TMSOTf prior to the reaction (see scheme; TMS=trimethylsilyl, Tf=trifluoromethanesulfonyl). This methodology can be applied to reduction and alkylation reactions, and enabled the short asymmetric total synthesis of (+)‐centrolobine with the highest overall yield reported to date.