Synthesis of (-)-LL-C10037α and Related Manumycin-Type Epoxyquinols

The manumycin-group metabolites

“…58 The racemic synthesis starts by preparing the core m-C 7 N unit of the final product. 132,133 Two similar routes starting from dimethoxyaniline produce the enamine 91, or its N-protected analogue as a pivotal intermediate. In the next step the 'upper' chain was introduced by coupling the appropriate acid chloride.…”

Recent advances in 1,4-benzoquinone chemistry

“…antibiotic LL-C10037a. [311][312][313] March et al 314 reported that phenylthiomonoketal (222) works efficiently as a masked p-benzoquinone in Diels-Alder reactions. These cycloadditions may be performed with certain Lewis acid catalyst like ZnBr 2 and give rise exclusively to endo adducts with a good to excellent anti-facial selectivity (Scheme 59).…”

An Efficient Regioselective and Diastereoselective Synthesis of the Epoxy-quinol Functionality as Building Block for the Manumycin Antibiotics by the Sequence of Photooxygenation, Reduction and Weitz-Scheffer Epoxidation

“…The significant discovery is that manumycins act as selective inhibitors of ras farnesyl transferase and might be of use in cancer chemotherapy. 7 However, in view of the metabolic instability of these natural products, it would seem that their potential as drugs should be limited; nonetheless, it has been established that the structurally related product LL-C10037a 8,9 without side chains possesses potent antitumor properties. The latter observation suggests that the complex side chains are not essential and, consequently, it should be worthwhile to prepare such simplified manumycin analogues, which might display useful biological activity.…”