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Published April 8, 2015 | Published + Supplemental Material
Journal Article Open

Phosphine-Catalyzed Enantioselective Intramolecular [3+2] Annulations To Generate Fused Ring Systems

Abstract

Substantial progress has been described in the development of asymmetric variants of the phosphine-catalyzed intermolecular [3+2] annulation of allenes with alkenes; however, there have not been corresponding advances for the intramolecular process, which can generate a higher level of complexity (an additional ring and stereocenter(s)). In this study, we describe the application of chiral phosphepine catalysts to address this challenge, thereby providing access to useful scaffolds that are found in bioactive compounds, including diquinane and quinolin-2-one derivatives, with very good stereoselectivity. The products of the [3+2] annulation can be readily transformed into structures that are even more stereochemically rich. Mechanistic studies are consistent with β addition of the phosphepine to the allene being the turnover-limiting step of the catalytic cycle, followed by a concerted [3+2] cycloaddition to the pendant olefin.

Additional Information

© 2015 American Chemical Society. ACS AuthorChoice - This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes. Received: February 23, 2015. Publication Date (Web): March 27, 2015. This work is dedicated to the memory of Gregory P. Harlow. Support has been provided by the National Institutes of Health (National Institute of General Medical Sciences: R01-GM57034), Dainippon Sumitomo Pharma Co., Ltd. (fellowship for Y.F.), Takeda Pharmaceutical Co. Ltd. (fellowship for A.N.), and the Swedish Research Council (fellowship for M.K.: Dnr 350-2012-6645). We thank Dr. Nathan D. Schley, Dr. Michael K. Takase (X-ray Crystallography Facility; a Bruker KAPPA APEX II X-ray diffractometer was purchased via NSF CRIF:MU award CHE-0639094), Dr. David G. VanderVelde (NMR Facility), Dr. Scott C. Virgil (Center for Catalysis and Chemical Synthesis, supported by the Gordon and Betty Moore Foundation), and Daniel T. Ziegler for assistance and for helpful discussions.

Attached Files

Published - jacs.5b01985.pdf

Supplemental Material - ja5b01985_si_001.cif

Supplemental Material - ja5b01985_si_002.pdf

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Created:
August 20, 2023
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October 23, 2023