CaltechAUTHORS
  A Caltech Library Service

Development of (Trimethylsilyl)ethyl Ester Protected Enolates and Applications in Palladium-Catalyzed Enantioselective Allylic Alkylation: Intermolecular Cross-Coupling of Functionalized Electrophiles

Reeves, Corey M. and Behenna, Douglas C. and Stoltz, Brian M. (2014) Development of (Trimethylsilyl)ethyl Ester Protected Enolates and Applications in Palladium-Catalyzed Enantioselective Allylic Alkylation: Intermolecular Cross-Coupling of Functionalized Electrophiles. Organic Letters, 16 (9). pp. 2314-2317. ISSN 1523-7060. PMCID PMC4011571. doi:10.1021/ol500355z. https://resolver.caltech.edu/CaltechAUTHORS:20140424-145313873

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

598kB
[img]
Preview
PDF - Supplemental Material
See Usage Policy.

3MB

Use this Persistent URL to link to this item: https://resolver.caltech.edu/CaltechAUTHORS:20140424-145313873

Abstract

The development of (trimethylsilyl)ethyl ester protected enolates is reported. The application of this class of compounds in palladium-catalyzed asymmetric allylic alkylation is explored, yielding a variety of α-quaternary six- and seven-membered ketones and lactams. Independent coupling partner synthesis engenders enhanced allyl substrate scope relative to traditional β-ketoester substrates; highly functionalized α-quaternary ketones generated by the union of (trimethylsilyl)ethyl β-ketoesters and sensitive allylic alkylation coupling partners serve to demonstrate the utility of this method for complex fragment coupling.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ol500355zDOIArticle
http://pubs.acs.org/doi/abs/10.1021/ol500355zPublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/ol500355zPublisherSupporting Information
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4011571/PubMed CentralArticle
ORCID:
AuthorORCID
Stoltz, Brian M.0000-0001-9837-1528
Additional Information:© 2014 American Chemical Society. 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 3, 2014; Publication Date (Web): April 11, 2014. The authors declare no competing financial interest. The authors wish to thank NIH-NIGMS (R01GM080269), Amgen, the Gordon and Betty Moore Foundation, the Caltech Center for Catalysis and Chemical Synthesis, and Caltech for financial support. C.M.R. thanks the Rose Hills Foundation for a predoctoral fellowship. The authors thank Scott Virgil (Caltech) for helpful discussions and instrumentation assistance. Rob Craig (Caltech) and Dr. Allen Hong (Caltech) are thanked for helpful discussion.
Funders:
Funding AgencyGrant Number
NIHR01GM080269-01
AmgenUNSPECIFIED
Gordon and Betty Moore FoundationUNSPECIFIED
Caltech Center for Catalysis and Chemical SynthesisUNSPECIFIED
CaltechUNSPECIFIED
Rose Hills FoundationUNSPECIFIED
Issue or Number:9
PubMed Central ID:PMC4011571
DOI:10.1021/ol500355z
Record Number:CaltechAUTHORS:20140424-145313873
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20140424-145313873
Official Citation:Development of (Trimethylsilyl)ethyl Ester Protected Enolates and Applications in Palladium-Catalyzed Enantioselective Allylic Alkylation: Intermolecular Cross-Coupling of Functionalized Electrophiles Corey M. Reeves, Douglas C. Behenna, and Brian M. Stoltz Organic Letters 2014 16 (9), 2314-2317
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:45195
Collection:CaltechAUTHORS
Deposited By: Aucoeur Ngo
Deposited On:25 Apr 2014 16:24
Last Modified:10 Nov 2021 17:01

Repository Staff Only: item control page