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Control of Enantioselectivity in Rhodium(I) Catalysis by Planar Chiral Dibenzo[ a , e ]cyclooctatetraenes
Author(s) -
Melcher MichaelaChristina,
Ivšić Trpimir,
Olag Charlotte,
Tenten Christina,
Lützen Arne,
Strand Daniel
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201704816
Subject(s) - stereocenter , rhodium , enantioselective synthesis , catalysis , chemistry , context (archaeology) , combinatorial chemistry , stereochemistry , organic chemistry , paleontology , biology
Planar chiral 5,11‐disubstiuted dibenzo[ a , e ]cyclo‐octatetraenes (dbCOTs) have been developed as the first useful chiral homologs to dbCOT‐ligands for asymmetric applications. Methods enabling the preparation of such compounds on a gram‐scale in enantiomerically pure form are described. Evaluated as ligands in rhodium(I)‐catalyzed 1,4‐ and 1,2‐arylation reactions, tertiary and quarternary stereogenic centers were formed with excellent yields and selectivities of up to >99 % ee . A catalytic asymmetric synthesis of a key cyclization precursor to (−)‐penifulvin A highlights the system in an applied context.