“…106 The key step in their approach was oxidative coupling of the methyl indol-3-ylacetate dianon to give diester 136 as a mixture of dl and meso forms, which were easily separated by crystallisation and chromatography. [107][108][109] Their initial approach was centred on formation of the indol-3-ylacetate trianion utilising similar chemistry, however it proved more fruitful to proceed via the dianion. The diester 136 was then subjected to imidation with benzylamine before an oxidative cyclisation gave N-benzyl protected arcyriaavin A 37.…”
Syntheses of indolo[2,3-a]pyrrolo[3,4-c]carbazole natural products are discussed, including staurosporine aglycone, arcyriaflavins, and glycosylated derivatives including staurosporine, rebeccamycin and K252A.
“…106 The key step in their approach was oxidative coupling of the methyl indol-3-ylacetate dianon to give diester 136 as a mixture of dl and meso forms, which were easily separated by crystallisation and chromatography. [107][108][109] Their initial approach was centred on formation of the indol-3-ylacetate trianion utilising similar chemistry, however it proved more fruitful to proceed via the dianion. The diester 136 was then subjected to imidation with benzylamine before an oxidative cyclisation gave N-benzyl protected arcyriaavin A 37.…”
Syntheses of indolo[2,3-a]pyrrolo[3,4-c]carbazole natural products are discussed, including staurosporine aglycone, arcyriaflavins, and glycosylated derivatives including staurosporine, rebeccamycin and K252A.
“…4 However, an electron transfer (ET) process appears to be much more likely. [5][6][7] In this case, the enolate 2 is oxidized with iodine by SET to give an initial radical cation which eliminates MI to afford radical 3, which may further react with [I] 2 • to give an a-iodocarbonyl compound 5. This can react with the excess of enolate present in solution by an S N 2 or SET pathway, affording the observed products 4.…”
Section: General Considerationsmentioning
confidence: 99%
“…Thus, the oxidative coupling of carboxylic acid dianions was inhibited when the amine arising from enolate generation with Li-amides was present in the reaction medium. 5,12 3 Stereoselective coupling of the enolates of carboxylic acid derivatives One of the key features of the oxidative dimerization reaction of carboxylic acid derivatives is the possibility of achieving a high degree of simple diastereoselectivity (syn+anti ratio). 13 This has been observed in the oxidative dimerization of the Li-dianions of carboxylic acids.…”
“…(3) Oxidative coupling of carboxylic acid. The third type oxidative coupling was developed by Belletire et al [10] in 1984. They employed the carboxylic acid compounds as the substrates and successfully achieved the homo-coupling products when lithium diisopropylamide (LDA) completed the hydrogen abstraction and I 2 acted as oxidant (Scheme 1c).…”
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