CaltechAUTHORS
  A Caltech Library Service

Catalytic, Enantioselective Aldol Additions with Methyl and Ethyl Acetate O-Silyl Enolates: A Chiral Tridentate Chelate as a Ligand for Titanium(IV)

Carreira, Erick M. and Singer, Robert A. and Lee, Wheeseong (1994) Catalytic, Enantioselective Aldol Additions with Methyl and Ethyl Acetate O-Silyl Enolates: A Chiral Tridentate Chelate as a Ligand for Titanium(IV). Journal of the American Chemical Society, 116 (19). pp. 8837-8838. ISSN 0002-7863. https://resolver.caltech.edu/CaltechAUTHORS:20180601-163441646

[img] PDF - Supplemental Material
See Usage Policy.

354Kb
[img] PDF - Supplemental Material
See Usage Policy.

1423Kb

Use this Persistent URL to link to this item: https://resolver.caltech.edu/CaltechAUTHORS:20180601-163441646

Abstract

Asymmetric catalysis of the Mukaiyama aldol reaction has been reported with complexes derived from Al, B, Sn(II), and Ti(IV). The levels of asymmetric induction for the addition of propionate-, isobutyrate-, and acetate-derived silyl thioketene acetals to aldehydes parallel those obtained with chiral-auxiliary-based methodologies. However, silyl ketene acetals derived from O-alkyl acetates uniformly provide aldolates possessing lower levels of asymmetric induction. We have initiated a study aimed at the design and synthesis of chiral Ti(IV) complexes that catalyze the enantioselective Mukaiyama aldol of O-trimethylsilyl, O-methyl, and O-ethyl ketene acetals with aldehydes. We report herein a catalyst that consists of a tridentate ligand derived from 3, Ti(O'^iPr)_4, and 3,5-di-tert-butylsalicylic acid. This catalyst (2-5 mol %) furnishes aldol adducts in good yields and high levels of asymmetric induction (88-97% ee).


Item Type:Article
Related URLs:
URLURL TypeDescription
https://dx.doi.org/10.1021/ja00098a065DOIArticle
https://pubs.acs.org/doi/suppl/10.1021/ja00098a065PublisherSupporting Information
ORCID:
AuthorORCID
Carreira, Erick M.0000-0003-1472-490X
Additional Information:© 1994 American Chemical Society. Received June 28, 1994. We are grateful to the Fannie and John Hertz Foundation for a Graduate Fellowship award to R.A.S. This research has been supported by a Beckman Young Investigator Award, a Camille and Henry Dreyfus New Faculty Award (NF-92-46), the Petroleum Research Fund (ACS-PRF 27091-G1), and a gift from the Medicinal Chemistry Research Unit at The Upjohn Company.
Funders:
Funding AgencyGrant Number
Fannie and John Hertz FoundationUNSPECIFIED
Arnold and Mabel Beckman FoundationUNSPECIFIED
Camille and Henry Dreyfus FoundationNF-92-46
American Chemical Society Petroleum Research FundACS-PRF 27091-G1
Upjohn CompanyUNSPECIFIED
Other Numbering System:
Other Numbering System NameOther Numbering System ID
Arnold and Mabel Beckman Laboratories of Chemical Synthesis8964
Issue or Number:19
Record Number:CaltechAUTHORS:20180601-163441646
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20180601-163441646
Official Citation:Catalytic, Enantioselective Aldol Additions with Methyl and Ethyl Acetate O-Silyl Enolates: A Chiral Tridentate Chelate as a Ligand for Titanium(IV) Erick M. Carreira, Robert A. Singer, and Wheeseong Lee Journal of the American Chemical Society 1994 116 (19), 8837-8838 DOI: 10.1021/ja00098a065
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:86768
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:04 Jun 2018 15:23
Last Modified:09 Mar 2020 13:18

Repository Staff Only: item control page