Total Synthesis of Cyathin A3 and Cyathin B2†
Keunho Kim
Department of Chemistry, Wayne State University, Detroit, MI 48236 (USA), Fax: (+1) 313-577-8822
Search for more papers by this authorJin Kun Cha Prof. Dr.
Department of Chemistry, Wayne State University, Detroit, MI 48236 (USA), Fax: (+1) 313-577-8822
Search for more papers by this authorKeunho Kim
Department of Chemistry, Wayne State University, Detroit, MI 48236 (USA), Fax: (+1) 313-577-8822
Search for more papers by this authorJin Kun Cha Prof. Dr.
Department of Chemistry, Wayne State University, Detroit, MI 48236 (USA), Fax: (+1) 313-577-8822
Search for more papers by this authorWe thank the NIH (GM 35956) for generous financial support. We also thank Dr. H. Oh for preliminary studies.
Abstract
Stereoselektiv verläuft die hier vorgestellte Synthese von Cyathin A3 und Cyathin B2 mithilfe einer Prins-Reaktion eines Cycloalkenylcyclopropanols. Erwähnung verdient auch die Anwendung einer Spirocyclobutanon-Einheit, um in einer effizienten Ringschlussmetathese stereoselektiv zu einem Siebenring mit dem gewünschten Funktionalisierungsmuster zu gelangen (siehe Schema).
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- 24Stereoselective reduction of 22 was achieved by L-Selectride to afford the corresponding β-alcohol at C14, the spectroscopic data of which were in excellent agreement with those of Nakada and co-workers.[9] Interestingly, this stereochemical outcome contrasts with the Nakada procedure under the control of the Corey–Bakshi–Shibata reagent.[25] Reduction of 2 with an excess of L-selectride gave small amounts of the corresponding β-diol at C14, along with large amounts of the primary alcohol (without ketone reduction; see Scheme 4). Reduction of 2 with diisobutylaluminum hydride gave a 1:3 mixture of the corresponding β- and α-diol, respectively.
- 25The enantiopure β-alcohol obtained from 22 was recently converted into (−)-3 and (−)-4 by Nakada and co-workers.[9] Albeit our alcohol product is racemic, this work can be viewed as a formal synthesis of 3 and 4.
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