Synthesis of Complex Diterpenes: Strategies Guided by Oxidation Pattern Analysis

Abstract

Scheme 2. Total Synthesis of (−)-Longikaurin E (3) and (−)-Trichorabdal A (2) Accounts of Chemical Research pubs.acs.org/accounts Article

Programmed Polyene Cyclization Enabled by Chromophore Disruption

“…6 Although the skeletal diversity of these diterpenes is localized within the C-ring, each motif is further differentiated through late-stage oxidative tailoring. 7 This added layer of complexity hinders the design of unified synthetic entry to this diverse collection of targets. Recent advances in synthetic biology have streamlined entry to this subgroup from more accessible terpenoid starting points.…”

Total Syntheses of the C19 Diterpenoid Alkaloids (−)-Talatisamine, (−)-Liljestrandisine, and (−)-Liljestrandinine by a Fragment Coupling Approach

“…As part of a larger program aimed at developing fragment coupling strategies to prepare structurally complex diterpenes, 30 we became interested in the C19 DTAs as synthetic targets. We envisioned that scission of 1 through the C10–C11 and C7–C8 bonds of the central B ring would disconnect the highly bridged hexacyclic framework into two fragments of similar size and complexity ( Figure 1 b, inset).…”

“…Beyond these bioinspired strategies, a number of other approaches to the C19 DTAs have been disclosed, 17−28 as well as an elegant synthesis by Gin and co-workers of the C18 norditerpenoid alkaloid neofinaconitine (not shown). 29 As part of a larger program aimed at developing fragment coupling strategies to prepare structurally complex diterpenes, 30 we became interested in the C19 DTAs as synthetic targets. We envisioned that scission of 1 through the C10− C11 and C7−C8 bonds of the central B ring would disconnect the highly bridged hexacyclic framework into two fragments of similar size and complexity (Figure 1b, inset).…”

Total Syntheses of the C19 Diterpenoid Alkaloids (–)-Talatisamine, (–)-Liljestrandisine, and (–)-Liljestrandinine by a Fragment Coupling Approach

“…Beyond these bioinspired strategies, a number of other approaches to the C19 DTAs have been disclosed, 12 as well as an elegant synthesis by Gin and coworkers of the C18 norditerpenoid alkaloid neofinaconitine (not shown). 13 As part of a larger program aimed at developing fragment coupling strategies to prepare structurally complex diterpenes, 14 we became interested in the C19 DTAs as synthetic targets. We envisioned that scission of 1 through the C10-C11 and C7-C8 bonds of the central B ring would disconnect the highly bridged hexacyclic framework into two fragments of similar size and complexity (Figure 1b, inset).…”