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Enantioselective Installation of Quaternary Centers in Cyclic Oxonitriles
Author(s) -
Gunes Yakup,
Arcelik Nejat,
Sahin Ertan,
Fleming Fraser F.,
Altundas Ramazan
Publication year - 2015
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201500895
Subject(s) - stereocenter , chemistry , enantioselective synthesis , alkoxide , allylic rearrangement , conjugate , alkyl , yield (engineering) , quaternary , stereochemistry , combinatorial chemistry , organic chemistry , catalysis , paleontology , materials science , mathematics , mathematical analysis , metallurgy , biology
Quaternary centers are rapidly and selectively installed in a series of seven‐membered and bridged cyclic oxonitriles through conjugate addition of an alkoxide to chloroalkenenitriles, followed by a Claisen rearrangement. Using this strategy, the stereogenic information of the carbinol in secondary allylic alcohols is transferred to the newly generated quaternary center. Experimentally, the sequence rapidly gives alkyl cyanocycloheptanones and bicycloalkanonecarbonitriles in good yield and with high selectivity, in a single synthetic operation.