Total Synthesis of Natural Products Containing a Bridgehead Double Bond

Summary Natural products with a bridgehead double bond, such as taxol and CP molecules, have long attracted considerable attention from chemists because of their promising bioactivity and structural complexity, with the high ring-strain energy in the ring systems representing a formidable synthetic challenge. Herein, strategies for the total synthesis of such complex natural products are reviewed for the first time by using 26 representative studies. Methods for constructing the bridged ring system and bridgehead double bond have been emphasized, including syntheses of the same natural product by different research groups using different strategies, to showcase the diversity of thought and creativity in this area. The total synthesis of these natural products not only provides precious bioactive substances and promising candidates for drug discovery but also has stimulated incredible advances in the development of new strategies and synthetic methods.