Triethylamine-Catalyzed Cyclization of Unsaturated Hydroperoxides in the Presence of Triethylammonium Hydrochloride: A Synthesis of 1,2-Dioxanes

John P. Stasiak; K. A. Woerpel

doi:10.1021/acs.orglett.4c04629

Triethylamine-Catalyzed Cyclization of Unsaturated Hydroperoxides in the Presence of Triethylammonium Hydrochloride: A Synthesis of 1,2-Dioxanes

John P. Stasiak, K. A. Woerpel

Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

Unsaturated hydroperoxides were synthesized from dienes using a regioselective cobalt-catalyzed hydroperoxidation reaction. Subsequent intramolecular oxa-Michael reactions in the presence of triethylammonium hydrochloride (HNEt₃Cl) and catalytic Et₃N formed 1,2-dioxanes, in several cases with high diastereoselectivity. These 1,2-dioxanes could be transformed to their respective carboxylic acids, without affecting the integrity of the peroxide linkage, to form compounds with structures that resemble biologically active natural products.

Original language	English (US)
Pages (from-to)	2037-2041
Number of pages	5
Journal	Organic Letters
Volume	27
Issue number	9
DOIs	https://doi.org/10.1021/acs.orglett.4c04629
State	Published - Mar 7 2025

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry

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title = "Triethylamine-Catalyzed Cyclization of Unsaturated Hydroperoxides in the Presence of Triethylammonium Hydrochloride: A Synthesis of 1,2-Dioxanes",

abstract = "Unsaturated hydroperoxides were synthesized from dienes using a regioselective cobalt-catalyzed hydroperoxidation reaction. Subsequent intramolecular oxa-Michael reactions in the presence of triethylammonium hydrochloride (HNEt3Cl) and catalytic Et3N formed 1,2-dioxanes, in several cases with high diastereoselectivity. These 1,2-dioxanes could be transformed to their respective carboxylic acids, without affecting the integrity of the peroxide linkage, to form compounds with structures that resemble biologically active natural products.",

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AU - Woerpel, K. A.

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AB - Unsaturated hydroperoxides were synthesized from dienes using a regioselective cobalt-catalyzed hydroperoxidation reaction. Subsequent intramolecular oxa-Michael reactions in the presence of triethylammonium hydrochloride (HNEt3Cl) and catalytic Et3N formed 1,2-dioxanes, in several cases with high diastereoselectivity. These 1,2-dioxanes could be transformed to their respective carboxylic acids, without affecting the integrity of the peroxide linkage, to form compounds with structures that resemble biologically active natural products.

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Triethylamine-Catalyzed Cyclization of Unsaturated Hydroperoxides in the Presence of Triethylammonium Hydrochloride: A Synthesis of 1,2-Dioxanes

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