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The stereoselective bromine\u2013lithium exchange that leads to the carbenoid <jats:bold>12<\/jats:bold> and the vinyllithium reagent <jats:bold>17\u2009a<\/jats:bold> on the one hand, and palladium\u2010catalyzed coupling reactions of the dibromoalkene <jats:bold>3<\/jats:bold> and the bromolactone <jats:bold>22<\/jats:bold> on the other are key steps en route to the butenolides <jats:bold>1<\/jats:bold> and <jats:bold>2<\/jats:bold>. The chiral building blocks (<jats:italic>S<\/jats:italic>)\u2010<jats:bold>3<\/jats:bold>, (<jats:italic>R<\/jats:italic>)\u2010<jats:bold>4<\/jats:bold>, and (<jats:italic>S<\/jats:italic>)\u2010<jats:bold>4<\/jats:bold> are readily available from (<jats:italic>R<\/jats:italic>)\u2010isopropylideneglyceraldehyde <jats:bold>5<\/jats:bold>, isobutyl (<jats:italic>R<\/jats:italic>)\u2010lactate <jats:bold>6\u2009a<\/jats:bold>, and ethyl (<jats:italic>S<\/jats:italic>)\u2010lactate <jats:bold>6\u2009b<\/jats:bold>, respectively. The synthetic procedure adopted here permits the absolute configuration of the natural products fugomycin (<jats:bold>1<\/jats:bold>) and desoxyfugomycin (<jats:bold>2<\/jats:bold>) to be assigned by comparison of their chiroptical properties with those of the synthetic products. The CD spectra of the bromolactone <jats:bold>22<\/jats:bold>, calculated by two different density functional methods (TDDFT, DFT\/MRCI), are found to be in good agreement with the measured spectra. On the basis of these calculations, the two CD bands observed could be assigned to n\u2013\u03c0* and \u03c0\u2013\u03c0* transitions, respectively. Fugomycin (<jats:bold>1<\/jats:bold>) and the synthetic butenolide <jats:bold>20<\/jats:bold> displayed high fungicidal activity against botrytis in greenhouse experiments, whereas the saturated lactone <jats:bold>21<\/jats:bold> was practically inactive.<\/jats:p>","DOI":"10.1002\/chem.200400132","type":"journal-article","created":{"date-parts":[[2004,8,2]],"date-time":"2004-08-02T12:20:33Z","timestamp":1091449233000},"page":"4584-4593","source":"Crossref","is-referenced-by-count":32,"title":["Synthesis and Determination of the Absolute Configuration of Fugomycin and Desoxyfugomycin: CD Spectroscopy and Fungicidal Activity of Butenolides"],"prefix":"10.1002","volume":"10","author":[{"given":"Manfred","family":"Braun","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Andreas","family":"Hohmann","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Jaykumar","family":"Rahematpura","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Corinna","family":"B\u00fchne","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Stefan","family":"Grimme","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2004,9,13]]},"reference":[{"key":"e_1_2_6_1_2","first-page":"280","volume-title":"Fungal Metabolites","author":"Turner B.","year":"1977"},{"key":"e_1_2_6_1_3","doi-asserted-by":"publisher","DOI":"10.1021\/cr60303a004"},{"key":"e_1_2_6_2_2","unstructured":"For reviews see: A. 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