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Bis-enolates with Extended π-Conjugation Are Powerful Nucleophiles: A Study of Their Alkylation Reactions with Very Hindered C-Electrophiles

Mariña Castroagudín, Rubén Lobato, Lucas Martínez-García, F Javier Sardina, M Rita Paleo

J Org Chem. 2019 Dec 20;84(24):15805-15816.

PMID: 31778066

Abstract:

Bis-enolates with extended π-conjugation, prepared by alkali metal-mediated reduction of several aromatic and unsaturated diesters, can be efficiently and regioselectively alkylated with very hindered C-electrophiles, such as neopentyl, secondary and tertiary alkyl halides, and tosylates. A one-step synthesis of 4-alkyl phthalates was derived from the reductive alkylation of a phthalate diester with hindered halides followed by rearomatization with oxygen. Additionally, synthetic protocols have been developed to efficiently prepare complex fused- or spiro-bicycles from diisopropyl phthalate in just one or two steps.

Chemicals Related in the Paper:

Catalog Number Product Name Structure CAS Number Price
AP605458 Diisopropyl phthalate Diisopropyl phthalate 605-45-8 Price
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