Construction of Vicinal Quaternary Centers via Ru-Catalyzed Enantiospecific Allylic Substitution with Lithium Ester Enolates

The installation of vicinal quaternary centers with absolute stereocontrol constitutes a considerable challenge in organic synthesis. Herein, we introduce a novel [Cp*Ru­(MeCN)3]­PF6/phenoxythiazoline catalyst system that achieves enantiospecific allylic substitution of tertiary carbonates with α,α-...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2024-08, Vol.146 (34), p.23674-23679
Main Authors: Papidocha, Sven M., Carreira, Erick M.
Format: Article
Language:English
Subjects:
catalysts
class
Lewis acids
Lewis bases
lithium
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Summary:The installation of vicinal quaternary centers with absolute stereocontrol constitutes a considerable challenge in organic synthesis. Herein, we introduce a novel [Cp*Ru­(MeCN)3]­PF6/phenoxythiazoline catalyst system that achieves enantiospecific allylic substitution of tertiary carbonates with α,α-disubstituted lithium ester enolates to give products containing vicinal quaternary centers. Noteworthy features include the direct use of nonstabilized ester enolates, a class of nucleophiles which has rarely been used in transition metal-catalyzed allylic substitution reactions. The approach is demonstrated for a broad scope of tertiary electrophiles as well as ester enolates and accomplishes stereoretentive substitution with excellent conservation of ee (89–99%) and branched/linear regioselectivities (up to 40:1).
ISSN:0002-7863
1520-5126
1520-5126
DOI:10.1021/jacs.4c07690