Controllable skeletal reorganizations in natural product synthesis

Abstract

This review highlights controllable skeletal reorganization, which involves the formation, cleavage, and migration of C–C and C–heteroatom bonds, as a powerful strategy in the efficient syntheses of steroid, terpenoid and alkaloid natural products.

Recent developments in the enzymatic modifications of steroid scaffolds

“…Many bioinspired total syntheses of biologically active steroids have been reported. 6,7 Meanwhile, the use of enzymes in biocatalytic processes offers high selectivity, efficiency, and sustainability. 8–11 Enzymatic modifications of steroids are being pursued, and efforts toward the identification of novel enzymes and protein engineering are crucial for enhancing enzyme selectivity and activity.…”

Strategic convergent synthesis en route to Veratrum steroidal alkaloids

“…These feedstocks are then transformed to the target NPs by harnessing skeletal rearrangement and/or selective C–C bond cleavage to edit the skeleton. 52–54 Additionally, various sp 3 C–H bond functionalization/oxidations 55 are employed to install the desired reactive functionalities onto the skeleton (Scheme 1Ca). 27 Given the limited availability of synthetic methods that allow for the desired chemical transformations in conjunction with the desired chemoselectivity, preparing highly functionalized complex NPs through semi-synthesis presents strategic and methodological challenges.…”

Rapid Access to Tigliane, Ingenane, and Rhamnofolane Diterpenes from a Lathyrane Precursor via Biomimetic Skeleton Transformation Strategy

“…Nonetheless, natural medicinal chemistry is always in pursuit of methods for quick access to natural products, improving scalability for the late-stage modification of natural skeletons. To address this issue, the major focus of natural products synthesis has switched to shortening synthetic routes and increasing overall yields . Herein, we propose a concise biomimetic skeleton transformation strategy to construct scarce Euphorbia diterpene skeletons from abundant natural products.…”