Kedarcidin Chromophore:  Synthesis of Its Proposed Structure and Evidence for a Stereochemical Revision

• Published in: Journal of the American Chemical Society Vol. 129; no. 17; pp. 5381 - 5383
• Main Authors: Ren, Feng, Hogan, Philip C, Anderson, Alan J, Myers, Andrew G
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 02.05.2007; Amer Chemical Soc
• Subjects: Antibiotics, Antineoplastic - chemical synthesis; Antibiotics, Antineoplastic - chemistry; Aza Compounds - chemistry; Chemistry; Chemistry, Multidisciplinary; Cycloparaffins - chemical synthesis; Cycloparaffins - chemistry; Enediynes - chemical synthesis; Enediynes - chemistry; Indicators and Reagents; Magnetic Resonance Spectroscopy; Mass Spectrometry; Molecular Conformation; Naphthalenes - chemical synthesis; Naphthalenes - chemistry; Physical Sciences; Science & Technology; Spectroscopy, Fourier Transform Infrared; Stereoisomerism; ENANTIOSELECTIVE SYNTHESIS; 2-METHYL-6-NITROBENZOIC ANHYDRIDE; ACIDS; ESTERS; SELECTIVE SYNTHESIS; AGLYCON; STRUCTURE ELUCIDATION; SUGAR
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja071205b

A convergent, enantioselective synthesis of the proposed structure of kedarcidin chromophore (1) is described. The route is 24 steps in the longest linear sequence (beginning with the commercial reagent 2,3-O-isopropylidene-d-erythronolactone) with an average yield of 75% per step (overall yield:  0.1%). Our 1H NMR data for 1 do not coincide with the data reported for kedarcidin chromophore. We have re-analyzed the original data and here propose a stereochemical revision at position C10, the site of attachment of the l-mycarose carbohydrate residue to the chromophore core (structure 2).