Modular Synthesis of a Versatile Double‐Allylation Reagent for Complex Diol Synthesis. Issue 29 (11th June 2021)

• Record Type: Journal Article
• Authors: Dorn, Stanna K.; Tharp, Annika E.; Brown, M. Kevin
• Is Part Of: Angewandte Chemie international edition. Volume 60:Issue 29(2021)
• Page Start: 16027
• Page End: 16034
• Publication Date: 2021-06-11
• Subjects: allylation -- boron -- carboboration -- catalysis -- copper; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202103435
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Double‐allylation reagents allow for the construction of highly complex molecules in an expedient fashion. We have developed an efficient, modular, and enantioselective approach towards accessing novel variants of these reagents through Cu/Pd‐catalyzed alkenylboration of alkenylboron derivatives. Importantly, we demonstrate novel use of an allylBdan reagent directly in a stereocontrolled allylation without initial deprotection to the boronic ester. These allylation products are employed in a second intermolecular allylation to access complex diol motifs, which has yet to be shown with these types of double‐allylation reagents. Overall, the modularity of this approach and the ease in which complex structural motifs can be accessed in a rapid manner signify the importance and utility of this method. Abstract : Make it a double: A strategy for the synthesis of novel double‐allylation reagents based on the alkenylboration of alkenylboronates is presented. The ease and modularity with which the reagents can be prepared allows rapid access to a variety of complex diol motifs. In the context of these studies, we also demonstrate the first examples of the use of boronamides in allylation reactions.