TY - CHAP
T1 - Complex Natural Products Derived from Pyrogallols
AU - Novak, Alexander J.E.
AU - Trauner, Dirk
N1 - Funding Information:
In 1945, Dewar published his groundbreaking assignments of the structures of stipitatic acid (8) and colchicine (9) (the correct regioisomer of colchicine would later be identified by King et al.), proposing that they both contain a cycloheptatrienone [11–13]. Dewar named these structures “tropolones” and the similarity in their reactivities provided support for the correct benzotropolone structure of purpurogallin (6), which was first proposed by Barltrop and Nicholson and shortly thereafter by Haworth, Moore, and Pauson (Fig. 3)[14, 15]. This assignment was supported by the studies of Caunt, Critchlow, Haworth, and coworkers who studied the reactivity, the degradation, and the synthesis of purpurogallin (6) from different starting materials [15–18]. Finally, in 1952 the structure of purpurogallin (6) was assigned unambiguously by X-ray crystallography by Dunitz, who showed that the benzotropolone structure first proposed by Barltrop and Nicholson was indeed correct [19].
Publisher Copyright:
© 2022, The Author(s), under exclusive license to Springer Nature Switzerland AG.
PY - 2022
Y1 - 2022
N2 - Pyrogallols (1,2,3-trihydroxybenzenes) are abundant in Nature, easily oxidized, and are central precursors to important natural products. The rich chemistry of their oxidized derivatives, the hydroxy-o-quinones, has been studied for over a century and still attracts the interest of the scientific community. Only in the last ten years have critical insights of pyrogallol chemistry from the mid-twentieth century been applied to modern natural product synthesis. Historical studies of pyrogallol chemistry, including [5+2], [4+2], and formal [5+5] cycloadditions are discussed here and reactivity guidelines established. The application and remarkable selectivity of these cycloadditions is then showcased in the recent syntheses of several fungal natural products, including dibefurin, epicolactone, the merocytochalasans, and preuisolactone A. The authors hope that this contribution will spark further interest in the fascinating chemistry of pyrogallols and natural products derived from them.
AB - Pyrogallols (1,2,3-trihydroxybenzenes) are abundant in Nature, easily oxidized, and are central precursors to important natural products. The rich chemistry of their oxidized derivatives, the hydroxy-o-quinones, has been studied for over a century and still attracts the interest of the scientific community. Only in the last ten years have critical insights of pyrogallol chemistry from the mid-twentieth century been applied to modern natural product synthesis. Historical studies of pyrogallol chemistry, including [5+2], [4+2], and formal [5+5] cycloadditions are discussed here and reactivity guidelines established. The application and remarkable selectivity of these cycloadditions is then showcased in the recent syntheses of several fungal natural products, including dibefurin, epicolactone, the merocytochalasans, and preuisolactone A. The authors hope that this contribution will spark further interest in the fascinating chemistry of pyrogallols and natural products derived from them.
KW - Cascades
KW - Cycloadditions
KW - Fungal metabolites
KW - o-Quinones
KW - Pyrogallols
KW - Racemic natural products
UR - http://www.scopus.com/inward/record.url?scp=85128135793&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85128135793&partnerID=8YFLogxK
U2 - 10.1007/978-3-030-92030-2_1
DO - 10.1007/978-3-030-92030-2_1
M3 - Chapter
C2 - 35416516
AN - SCOPUS:85128135793
T3 - Progress in the Chemistry of Organic Natural Products
SP - 1
EP - 46
BT - Progress in the Chemistry of Organic Natural Products
PB - Springer Science and Business Media Deutschland GmbH
ER -