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Iridium-Catalyzed Enantioselective Allylic Substitution of Aliphatic Esters with Silyl Ketene Acetals as the Ester Enolates.
Angew Chem Int Ed Engl. 2017 07 17; 56(30):8887-8891.AC

Abstract

Enantioselective allylic substitution with enolates derived from aliphatic esters under mild conditions remains challenging. Herein we report iridium-catalyzed enantioselective allylation reactions of silyl ketene acetals, the silicon enolates of esters, to form products containing a quaternary carbon atom at the nucleophile moiety and a tertiary carbon atom at the electrophile moiety. Under relatively neutral conditions, the allylated aliphatic esters were obtained with excellent regioselectivity and enantioselectivity. These products were readily converted into primary alcohols, carboxylic acids, amides, isocyanates, and carbamates, as well as tetrahydrofuran and γ-butyrolactone derivatives, without erosion of enantiomeric purity.

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Authors+Show Affiliations

Jiang X
Department of Chemistry, University of California, Berkeley, CA, 94720, USA.
Hartwig JF
Department of Chemistry, University of California, Berkeley, CA, 94720, USA.

MeSH

AcetalsAllyl CompoundsCatalysisEstersEthylenesIridiumKetonesMolecular StructureSilanesStereoisomerism

Pub Type(s)

Journal Article
Research Support, N.I.H., Extramural

Language

eng

PubMed ID

28597600

Citation

Jiang, Xingyu, and John F. Hartwig. "Iridium-Catalyzed Enantioselective Allylic Substitution of Aliphatic Esters With Silyl Ketene Acetals as the Ester Enolates." Angewandte Chemie (International Ed. in English), vol. 56, no. 30, 2017, pp. 8887-8891.
Jiang X, Hartwig JF. Iridium-Catalyzed Enantioselective Allylic Substitution of Aliphatic Esters with Silyl Ketene Acetals as the Ester Enolates. Angew Chem Int Ed Engl. 2017;56(30):8887-8891.
Jiang, X., & Hartwig, J. F. (2017). Iridium-Catalyzed Enantioselective Allylic Substitution of Aliphatic Esters with Silyl Ketene Acetals as the Ester Enolates. Angewandte Chemie (International Ed. in English), 56(30), 8887-8891. https://doi.org/10.1002/anie.201704354
Jiang X, Hartwig JF. Iridium-Catalyzed Enantioselective Allylic Substitution of Aliphatic Esters With Silyl Ketene Acetals as the Ester Enolates. Angew Chem Int Ed Engl. 2017 07 17;56(30):8887-8891. PubMed PMID: 28597600.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Iridium-Catalyzed Enantioselective Allylic Substitution of Aliphatic Esters with Silyl Ketene Acetals as the Ester Enolates. AU - Jiang,Xingyu, AU - Hartwig,John F, Y1 - 2017/06/27/ PY - 2017/04/27/received PY - 2017/6/10/pubmed PY - 2019/3/12/medline PY - 2017/6/10/entrez KW - alkylation KW - asymmetric catalysis KW - enantioselectivity KW - esters KW - iridium SP - 8887 EP - 8891 JF - Angewandte Chemie (International ed. in English) JO - Angew Chem Int Ed Engl VL - 56 IS - 30 N2 - Enantioselective allylic substitution with enolates derived from aliphatic esters under mild conditions remains challenging. Herein we report iridium-catalyzed enantioselective allylation reactions of silyl ketene acetals, the silicon enolates of esters, to form products containing a quaternary carbon atom at the nucleophile moiety and a tertiary carbon atom at the electrophile moiety. Under relatively neutral conditions, the allylated aliphatic esters were obtained with excellent regioselectivity and enantioselectivity. These products were readily converted into primary alcohols, carboxylic acids, amides, isocyanates, and carbamates, as well as tetrahydrofuran and γ-butyrolactone derivatives, without erosion of enantiomeric purity. SN - 1521-3773 UR - https://www.unboundmedicine.com/medline/citation/28597600/Iridium_Catalyzed_Enantioselective_Allylic_Substitution_of_Aliphatic_Esters_with_Silyl_Ketene_Acetals_as_the_Ester_Enolates_ DB - PRIME DP - Unbound Medicine ER -