Bond formations by intermolecular and intramolecular trappings of acylketenes and their applications in natural product synthesis.
The reactive intermediates known as acylketenes exhibit a rich chemistry and have been extensively utilized for many types of inter- and intramolecular bond-forming reactions within the field of organic synthesis. Characteristic reactions of acylketenes include cycloadditions, carbon-carbon bond-forming reactions, and nucleophilic capture with alcohols or amines to give beta-keto acid derivatives. In particular, the intramolecular capture of acylketene intermediates with pendant nucleophiles represents a powerful method for forming both medium-sized rings and macrocycles, often in high yield. This tutorial review examines the history, generation, and reactivity of acylketenes with a special focus on their applications in the synthesis of natural products.
Princeton University, Princeton, NJ, USA. kreber@princeton.edu
Keith P
KP
Reber
S David
SD
Tilley
Erik J
EJ
Sorensen
D000438:Alcohols / Q000737:chemistry; D000475:Alkenes / Q000737:chemistry; D000588:Amines / Q000737:chemistry; D001688:Biological Products / Q000138:chemical synthesis*; D007659:Ketones / Q000737:chemistry
D000438:Alcohols; D000475:Alkenes; D000588:Amines; D001688:Biological Products; D007659:Ketones