Formal total synthesis of enigmazole A. Issue 51 (19th December 2018)

• Record Type: Journal Article
• Authors: Meissner, Andreas; Kishi, Takayuki; Fujisawa, Yuka; Murai, Yuto; Takamura, Hiroyoshi; Kadota, Isao
• Is Part Of: Tetrahedron letters. Volume 59:Issue 51(2018)
• Page Start: 4492
• Page End: 4495
• Publication Date: 2018-12-19
• Subjects: Enigmazole A -- Total synthesis -- Convergent synthesis -- Macrolide -- Allylation -- Reductive acetylation; Chemistry, Organic -- Periodicals; 547.005
• DOI: 10.1016/j.tetlet.2018.11.017
• Languages: English
• ISSNs: 0040-4039

Abstract

Graphical abstract: Highlights: Reporting a formal total synthesis of enigmazole A, a cytotoxic macrolide. The 2, 6-disubstituted methylene THP moiety was constructed by the intramolecular allylation of an α-acetoxy ether derivative. A convergent synthesis of the macrolide structure was accomplished. Abstract: A stereoselective formal total synthesis of enigmazole A, a marine macrolide isolated from Cinachyrella enigmatica, is described. Lewis acid mediated intramolecular allylation of an α-acetoxy ether, prepared from alcohol and carboxylic acid fragments was carried out to construct the methylene THP ring with high stereoselectivity. The late-stage macrolactonization of the corresponding seco-acid provided a known synthetic intermediate of enigmazole A.