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Carbonylierende Ringerweiterung, 5. Enantioselektive Synthese des Bicyclo[3.2.1]oct‐3‐en‐2,8‐dion‐Systems durch doppelte Carbonylierung von α‐Terpinen und anderen prochiralen Cyclohexadienen
Author(s) -
Eilbracht Peter,
Hittinger Christel,
Kufferath Klaus,
Schmitz Anja,
Gilsing HansDetlev
Publication year - 1990
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19901230523
Subject(s) - chemistry , bicyclic molecule , stereochemistry , steric effects , ene reaction , chirality (physics) , ylide , enantioselective synthesis , medicinal chemistry , organic chemistry , catalysis , chiral symmetry breaking , physics , quantum mechanics , nambu–jona lasinio model , quark
Carbonylating Ring Enlargement, 5 1) . – Enantioselective Synthesis of the Bicyclo[3.2.l]oct‐3‐ene‐2,8‐dione Systems by Double Carbonylation of α‐Terpinene and Other Prochiral Cyclohexadienes The steric information in tricarbonyl iron complexes of type 2 (R 1 ≠ R 2 ), established during the complexation of prochiral 1,3‐cyclohexadienes can be transferred to bicyclo[3.2.1]oct‐3‐ene‐2,8‐diones by metal‐induced ring enlargement and bridging carbonylation. This was verified by the synthesis and conversion of optically active tricarbonyl iron complexes 2 of α‐terpinene ( 1 ). These complexes can be either obtained by chirality transfer during complexation and rearrangement of ( R )‐(+)‐ or ( S )‐(‐)‐limonene ( 7 ) or by separation of racemic mixtures on triacetyl cellulose. The separation on chiral phases and subsequent stereoselective conversion to bicyclo[3.2.1]oct‐3‐ene‐2,8‐diones may also be carried out with other tricarbonyl iron complexes of prochiral cyclohexadienes (lacking additional functional groups).