Mg. Banwell et al., FULLY REGIOCONTROLLED SYNTHESIS OF (PLUS-OR-MINUS)-12A,12B-SECOCOLCHICINE AND STUDIES CONCERNING ITS CYCLIZATION TO THE ALKALOID COLCHICINE, Journal of the Chemical Society. Perkin transactions. I, (22), 1993, pp. 2817-2830
A fully regiocontrolled synthesis of the title compound 6, an AC-ring
analogue of the alkaloid colchicine 1, is reported. The key step assoc
iated with the sequence used was condensation of lithium halogenocarbe
noid 10-a synthetic equivalent for the inaccessible 7-methoxytropon-3-
yl anion 12- with 3,4,5-trimethoxycinnamaldehyde 17 to produce the 1,2
-addition product 18 as a mixture of diastereoisomers. Elaboration of
compound 18 provided benzoate 23 which, on treatment with base, underw
ent ring-expansion to give troponoid 24 in excellent yield. Replacemen
t of the C-7 benzoate group in compound 24 by an acetamido moiety was
readily achieved and produced compound 6 in good overall yield. Unsucc
essful attempts to convert compound 6 and the deacetamido analogue 38
into colchicine and deacetamidocolchicine 3, respectively, are describ
ed.