合成路线1

An asymmetric synthesis of (-)-quinocarcin has been described: The acylation of 2-(2-methoxy-6-methylphenyl)-(R)- glycinol (I) with maleic anhydride (II) in ether gives the maleic monoamide (III), which is cyclized to the pyrrolidinedione (IV) by refluxing with acetic anhydride. The cyclization of (IV) with methyl azide in toluene affords the pyrrolotriazole (V), which is irradiated with UV light (Hg lamp), giving the aziridinopyrrole (VI). The cycloaddition of (VI) with the chiral acrylamide (VII) affords the diazabicyclo[3.2.1]octane (VIII). At this point, the hydroxyl group of (VIII) is protected with methoxymethyl chloride giving the methoxymethyl ether (IX), which is submitted to benzylic bromination with N-bromosuccinimide (NBS) in chloroform, yielding the bromo derivative (X). The reaction of (X) with triphenylphosphine affords the phosphonium salt (XI), which by treatment with potassium tert-butoxide and heat cyclizes to the tetracyclo compound (XII). Hydrogenation of (XII) with H2 over RaNi in ethanol affords the reduced compound (XIII), which is treated with LiOH in THF - water, affording the free acid derivative (XIV). The deprotection of the ether group of (XIV) with trimethylsilyl chloride and NaI in acetonitrile gives the hydroxymethyl derivative (XV), which is finally cyclized to (-)-quinocarcin with AgNO3 in methanol-water.