TY - JOUR

T1 - Synthesis of Swinhoeisterol A, Dankasterone A and B, and Periconiastone A by Radical Framework Reconstruction

AU - Duecker, Fenja L.

AU - Heinze, Robert C.

AU - Heretsch, Philipp

N1 - Funding Information: Financial support for this work was provided by Deutsche Forschungsgemeinschaft (Grant No. HE 7133/7-1), the Boehringer Ingelheim Stiftung (exploration grant to P.H.), and Studienstiftung des Deutschen Volkes (Ph.D. scholarship to R.C.H.). We acknowledge the assistance of the Core Facility BioSupraMol supported by the DFG. We are grateful to Mira Mueller for experimental assistance, to Christiane Groneberg for HPLC separations, and to Prof. Dr. Dieter Lentz for X-ray crystallographic analyses (Freie Universität Berlin).

PY - 2020/1/8

Y1 - 2020/1/8

N2 - A switchable radical framework reconstruction approach to structurally unique 13(14 → 8),14(8 → 7)diabeo-steroid swinhoeisterol A was developed. The conversion of an ergostane skeleton proceeded through the intermediacy of a 13(14 → 8)abeo-framework as present in the dankasterone and periconiastone family of natural products and features a β scission of a 14-alkoxy radical with concomitant generation of the C8-C13 bond. From this intermediate, and dependent on the conditions employed, the cascade continues with a Dowd-Beckwith rearrangement and leads to the formation of the 13(14 → 8),14(8 → 7)diabeo-framework of the swinhoeisterol class of natural products. The synthesis of these frameworks then allowed for efficient access to swinhoeisterol A (1), dankasterone A (Δ 4-2), dankasterone B (2), and periconiastone A (3).

AB - A switchable radical framework reconstruction approach to structurally unique 13(14 → 8),14(8 → 7)diabeo-steroid swinhoeisterol A was developed. The conversion of an ergostane skeleton proceeded through the intermediacy of a 13(14 → 8)abeo-framework as present in the dankasterone and periconiastone family of natural products and features a β scission of a 14-alkoxy radical with concomitant generation of the C8-C13 bond. From this intermediate, and dependent on the conditions employed, the cascade continues with a Dowd-Beckwith rearrangement and leads to the formation of the 13(14 → 8),14(8 → 7)diabeo-framework of the swinhoeisterol class of natural products. The synthesis of these frameworks then allowed for efficient access to swinhoeisterol A (1), dankasterone A (Δ 4-2), dankasterone B (2), and periconiastone A (3).

UR - http://www.scopus.com/inward/record.url?scp=85077676480&partnerID=8YFLogxK

U2 - 10.1021/jacs.9b12899

DO - 10.1021/jacs.9b12899

M3 - Article

VL - 142

SP - 104

EP - 108

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 1

ER -