A stereoselective construction of a cis-1,2-oxazadecaline skeleton using a substrate-controlled intramolecular oxy-Michael addition of tyrosine-derived hydroxylamines

• Published in: Tetrahedron letters Vol. 61; no. 4; p. 151412
• Main Authors: Kimishima, Atsushi, Saito, Hayato, Yamaguchi, Ayuta, Arai, Masayoshi
• Format: Journal Article
• Language: English
• Published: Elsevier Ltd 23-01-2020
• Subjects: 1,3-Allylic strain; cis-1,2-Oxazadecaline; Intramolecular oxy-Michael addition; Oxidative dearomatization; 1,3-Allylic strain; Oxidative dearomatization; cis-1,2-Oxazadecaline; Intramolecular oxy-Michael addition
• ISSN: 0040-4039; 1873-3581
• DOI: 10.1016/j.tetlet.2019.151412

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•New deprotection-triggered intramolecular oxy-Michael addition for the construction of cis-1,2-oxazadecaline frameworks.•An eight-step synthesis of the optically active cis-1,2-oxazadecaline enone from corresponding tyrosine esters.•A1,3 strain-involved plausible reaction mechanism.•Potential use of the strategy for the synthesis of trichodermamide type alkaloids.
A method for the stereoselective construction of cis-1,2-oxazadecaline skeletons via a substrate-controlled intramolecular oxy-Michael addition of readily available tyrosine-derived hydroxylamines has been developed. The approach features an eight-step synthesis of the optically active cis-1,2-oxazadecaline enones from tyrosine esters. The described chiral pool synthetic strategy has great potential for the efficient enantioselective synthesis of natural products possessing cis-1,2-oxazadecaline frameworks, such as trichodermamides.