A Caltech Library Service

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

Lee, Sarah Yunmi and Fujiwara, Yuji and Nishiguchi, Atsuko and Kalek, Marcin and Fu, Gregory C. (2015) Phosphine-Catalyzed Enantioselective Intramolecular [3+2] Annulations To Generate Fused Ring Systems. Journal of the American Chemical Society, 137 (13). pp. 4587-4591. ISSN 0002-7863. PMCID PMC4433041. doi:10.1021/jacs.5b01985.

[img] PDF (ACS AuthorChoice) - Published Version
See Usage Policy.

[img] PDF (Experimental procedures and compound characterization data) - Supplemental Material
See Usage Policy.

[img] Crystallographic Info File (CIF) - Supplemental Material
See Usage Policy.


Use this Persistent URL to link to this item:


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.

Item Type:Article
Related URLs:
URLURL TypeDescription Information CentralArticle
Lee, Sarah Yunmi0000-0003-4531-9392
Kalek, Marcin0000-0002-1595-9818
Fu, Gregory C.0000-0002-0927-680X
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.
Funding AgencyGrant Number
Dainippon Sumitomo Pharma Co., Ltd.UNSPECIFIED
Takeda Pharmaceutical Co. Ltd.UNSPECIFIED
Swedish Research Council350-2012-6645
Gordon and Betty Moore FoundationUNSPECIFIED
Issue or Number:13
PubMed Central ID:PMC4433041
Record Number:CaltechAUTHORS:20150406-090131028
Persistent URL:
Official Citation:Phosphine-Catalyzed Enantioselective Intramolecular [3+2] Annulations To Generate Fused Ring Systems Sarah Yunmi Lee, Yuji Fujiwara, Atsuko Nishiguchi, Marcin Kalek, and Gregory C. Fu Journal of the American Chemical Society 2015 137 (13), 4587-4591 DOI: 10.1021/jacs.5b01985
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:56369
Deposited By: Tony Diaz
Deposited On:06 Apr 2015 20:06
Last Modified:08 Jun 2022 17:49

Repository Staff Only: item control page