New stereoselective route to the epoxyquinol core of manumycin-type natural products. Synthesis of enantiopure (+)-bromoxone, (-)-LL-C10037 alpha, and (+)-KT 8110.
A practical route is decribed for the preparation of the C(7)N core of manumycin-type compounds. Starting from p-benzoquinone, optically pure compounds in both forms can be prepared via enzymatic resolution of a derived diacetoxy conduritol. A diepoxy aminoinositol is accessible which can function for formation of enantiopure epoxyquinones and quinols. Examples are given for acylation reactions of this amine with several acyl derivatives. With this approach (-)-LL-C10037alpha and quinones such as (+)-KT-8110 with 5R,6S-configuration can be synthesized through oxidation. In addition a short route to (+)-bromoxone is described. Most steps include simple epoxide formation and cleavage reactions which all can be carried out in a high stereoselective manner.
Block
O
O
Fachbereich Chemie, Bergische Universität-Gesamthochschule Wuppertal, Gauss-trasse 20, D-42097 Wuppertal, Germany.
Klein
G
G
Altenbach
H J
HJ
Brauer
D J
DJ
D019086:Bridged Bicyclo Compounds, Heterocyclic / Q000138:chemical synthesis*; D004852:Epoxy Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D006873:Hydroquinones / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D011090:Polyenes / Q000737:chemistry*; D053284:Polyunsaturated Alkamides; D011809:Quinones / Q000138:chemical synthesis*; D013237:Stereoisomerism
D019086:Bridged Bicyclo Compounds, Heterocyclic; D004852:Epoxy Compounds; D006873:Hydroquinones; C415027:KT 8110; D011090:Polyenes; D053284:Polyunsaturated Alkamides; D011809:Quinones; C415026:bromoxone; C043671:LL-C 10037alpha; C054474:manumycin