1996
DOI: 10.1021/jo961529a
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Exploratory Synthetic Studies of the α-Methoxylation of Amides via Cuprous Ion-Promoted Decomposition of o-Diazobenzamides

Abstract: A convenient nonelectrochemical amide oxidation method has been developed. The process involves a cuprous ion-promoted decomposition of o-diazobenzamides like 4, generated in situ from the corresponding o-aminobenzamides, to give N-acyliminium ion intermediate 9 via a 1,5-H-atom transfer, followed by metal-catalyzed oxidation of the resulting α-amidyl radical. The transformation produces α-methoxybenzamides 15 in good yields. An attempt was made to apply this oxidation method to a total synthesis of the alkalo… Show more

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Cited by 95 publications
(37 citation statements)
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“…[20,21] Importantly, if the aromatic substituent bears a paramethoxy substituent (such as in substrates 5 o-s and 6 o), smooth cleavage of the aromatic residue can be achieved under mild conditions, [22] thus providing suitably functionalized, synthetically useful amines 7 a-f in high yields (Scheme 5). [23] Finally, the synthetic utility of the method outlined herein is showcased in the context of the total synthesis of the natural product (AE)-indolizidine 167B. [24] As depicted in Scheme 6, alkylation of pyrrolidine 8 with 2-fluoro-4-methoxybenzaldehyde 9, followed by sequential treatment with 20 mol % of Sc(OTf) 3 and the Grignard reagent 10 afforded the anisidine intermediate 11, [25] with an overall yield of 43 % for the three steps.…”
Section: Methodsmentioning
confidence: 99%
“…[20,21] Importantly, if the aromatic substituent bears a paramethoxy substituent (such as in substrates 5 o-s and 6 o), smooth cleavage of the aromatic residue can be achieved under mild conditions, [22] thus providing suitably functionalized, synthetically useful amines 7 a-f in high yields (Scheme 5). [23] Finally, the synthetic utility of the method outlined herein is showcased in the context of the total synthesis of the natural product (AE)-indolizidine 167B. [24] As depicted in Scheme 6, alkylation of pyrrolidine 8 with 2-fluoro-4-methoxybenzaldehyde 9, followed by sequential treatment with 20 mol % of Sc(OTf) 3 and the Grignard reagent 10 afforded the anisidine intermediate 11, [25] with an overall yield of 43 % for the three steps.…”
Section: Methodsmentioning
confidence: 99%
“…[*] Dr. [23] Abschließend konnten wir den präparativen Nutzen der hier beschriebenen Methode an einer Totalsynthese des Naturstoffs (AE)-Indolizidin 167B demonstrieren. Generell sollte in unsymmetrisch substituierten Hydriddonoren die Übertragung bevorzugt zum am besten stabilisierten Karbokation ablaufen.…”
unclassified
“…13f To further confirm the stereochemistry at the newly formed stereogenic centre the cyclised product 13 was converted into dimethoxy compound 14, whose 1 H NMR spectra were in agreement with the reported values. 15 Compound 13 was subjected to hydrogenation in the presence of Pd/C, which resulted in the formation of 2a. The specific rotation of the C-2 epimer of (+)-deacetylanisomycin 2a was ½a 25 D ¼ þ18 (c 0.8, MeOH), {lit 12d ½a 25 D ¼ þ20 (c 1, MeOH)}.…”
Section: Resultsmentioning
confidence: 99%