CaltechAUTHORS
  A Caltech Library Service

Enantioselective Organo-Cascade Catalysis

Huang, Yong and Walji, Abbas M. and Larsen, Catharine H. and MacMillan, David W. C. (2005) Enantioselective Organo-Cascade Catalysis. Journal of the American Chemical Society, 127 (43). pp. 15051-15053. ISSN 0002-7863. https://resolver.caltech.edu/CaltechAUTHORS:20170512-123545439

[img] PDF (Experimental procedures, structural proofs, and spectral data for all new compounds) - Supplemental Material
See Usage Policy.

156Kb

Use this Persistent URL to link to this item: https://resolver.caltech.edu/CaltechAUTHORS:20170512-123545439

Abstract

A new strategy for organocatalysis based on the biochemical blueprints of biosynthesis has enabled a new laboratory approach to cascade catalysis. Imidazolidinone-based catalytic cycles, involving iminium and enamine activation, have been successfully combined to allow a large diversity of nucleophiles (furans, thiophenes, indoles, butenolides, hydride sources, tertiary amino lactone equivalents) and electrophiles (fluorinating and chlorinating reagents) to undergo sequential addition with a wide array of α,β-unsaturated aldehydes. These new cascade catalysis protocols allow the invention of enantioselective transformations that were previously unknown, including the asymmetric catalytic addition of the elements of HF across a trisubstituted olefin. Importantly, these domino catalysis protocols can be mediated by a single imidazolidinone catalyst or using cycle-specific amine catalysts. In the latter case, cascade catalysis pathways can be readily modulated to provide a required diastereo- and enantioselective outcome via the judicious selection of the enantiomeric series of the amine catalysts. A central benefit of combining multiple asymmetric organocatalytic events into one sequence is the intrinsic requirement for enantioenrichment in the second induction cycle, as demonstrated by the enantioselectivities obtained throughout this study (≥99% ee in all cases).


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ja055545dDOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja055545dPublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/ja055545dPublisherSupporting Information
ORCID:
AuthorORCID
Huang, Yong0000-0002-7963-0720
Additional Information:© 2005 American Chemical Society. Received August 14, 2005. Publication Date (Web): October 6, 2005. Financial support was provided by the NIHGMS (R01 GM66142-01) and kind gifts from Amgen and Merck. C.H.L. is a NDSEG predoctoral fellow.
Funders:
Funding AgencyGrant Number
NIHR01 GM66142-01
AmgenUNSPECIFIED
MerckUNSPECIFIED
National Defense Science and Engineering Graduate (NDSEG) FellowshipUNSPECIFIED
Issue or Number:43
Record Number:CaltechAUTHORS:20170512-123545439
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20170512-123545439
Official Citation:Enantioselective Organo-Cascade Catalysis Yong Huang, Abbas M. Walji, Catharine H. Larsen, and David W. C. MacMillan Journal of the American Chemical Society 2005 127 (43), 15051-15053 DOI: 10.1021/ja055545d
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:77413
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:12 May 2017 23:32
Last Modified:09 Mar 2020 13:18

Repository Staff Only: item control page