DOI: 10.1021/acs.joc.6c02174 ISSN: 0022-3263
Further Insights into the Stereoselective Total Synthesis of Ageliferin via Dearomatizing Diels–Alder Cycloaddition
Yudai Fujino, Ayami Amano, Taisei Matoba, Keisuke Fukaya, Daisuke UrabeAbstract
We report the total synthesis of ageliferin, focusing on the preparation of substrate for the D-tartrate-tethered cycloaddition and late-stage transformations. A D-tartrate-derived tether was designed to facilitate a challenging intramolecular dearomative Diels–Alder reaction of the hymenidin-derived units. The key cycloaddition proceeded with complete diastereoselectivity to construct the highly functionalized six-membered framework bearing three contiguous stereocenters. Conversion of the cycloadduct to ageliferin required careful adjustment of the reaction sequence, including protecting-group manipulations, introduction of azido groups onto the imidazole rings, cleavage of the N–N bond, and installation of the pyrrole-2-carbonyl units.