Wiley InterScience Backfile Collection 1832-2000
Chemistry and Pharmacology
Carbonylating Ring Enlargement, 51). - Enantioselective Synthesis of the Bicyclo[3.2.l]oct-3-ene-2,8-dione Systems by Double Carbonylation of α-Terpinene and Other Prochiral CyclohexadienesThe steric information in tricarbonyl iron complexes of type 2(R1 ≠ R2), 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).
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