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Symbiotic reagent activation: Oppenauer oxidation of magnesium alkoxides by silylglyoxylates triggers second-stage aldolization.

ABSTRACT: The treatment of silylglyoxylates with magnesium alkoxides at ambient temperature results in symbiotic Oppenauer oxidation of the alkoxide and Meerwein-Ponndorf-Verley reduction of the silylglyoxylate. The reduced silylglyoxylate undergoes subsequent [1,2]-Brook rearrangement and aldol reaction with the carbonyl oxidation product. The magnesium alkoxide may be accessed via deprotonation of primary or secondary alcohols with EtMgBr, via addition of Grignard reagents to aldehydes, or via CuI-catalyzed alkylation of epoxides. For aliphatic primary alkoxides, moderate levels of anti diastereoselection are observed. A crossover experiment reveals that dissociation of the nascent aldehyde from the magnesium center is faster than [1,2]-Brook rearrangement and aldolization.

SUBMITTER: Linghu X

PROVIDER: S-EPMC1868421 | biostudies-literature | 2006 Jul

REPOSITORIES: biostudies-literature

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Symbiotic reagent activation: Oppenauer oxidation of magnesium alkoxides by silylglyoxylates triggers second-stage aldolization.

Linghu Xin X Satterfield Andrew D AD Johnson Jeffrey S JS

Journal of the American Chemical Society 20060701 29

The treatment of silylglyoxylates with magnesium alkoxides at ambient temperature results in symbiotic Oppenauer oxidation of the alkoxide and Meerwein-Ponndorf-Verley reduction of the silylglyoxylate. The reduced silylglyoxylate undergoes subsequent [1,2]-Brook rearrangement and aldol reaction with the carbonyl oxidation product. The magnesium alkoxide may be accessed via deprotonation of primary or secondary alcohols with EtMgBr, via addition of Grignard reagents to aldehydes, or via CuI-catal ...[more]

PMID: 16848444

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