Recent Total Syntheses of Cephalotaxine‐Type Alkaloids and Their Structural Diversification (2021–2024): An Update

Abstract

Cephalotaxine‐type alkaloids present a challenging yet rewarding target for synthetic chemists due to their intricate polycyclic structures and significant biological activity. This review consolidates recent reports (2021–2024) on the total synthesis of cephalotaxine‐type alkaloids, emphasizing innovative catalytic approaches and key transformations that enable efficient construction of the core tetracyclic framework. Advances in techniques such as asymmetric polycyclization, dual catalysis, and rearrangement strategies have streamlined synthetic routes, reducing the number of steps and enhancing stereocontrol. Additionally, structural diversification on the cephalotaxine scaffold during this period has offered valuable insights into structural modifications in medicinal chemistry and potential biosynthetic pathways. This review proposes a new structural classification of cephalotaxine‐type alkaloids. It covers ten recent total syntheses, providing detailed descriptions of the synthetic methodologies employed and comparative analyses with previous syntheses. Four reports on the structural diversification of cephalotaxines are also included.