Wittig indole synthesis

The ring closure (83 — 84) involves an intramolecular Wittig reaction (81CC14). Another variation on the Madelung indole synthesis is provided by the cyclization of o-isocyanobenzenes (85 — 86) (77JA3532). 

Kraus and his group extended their Wittig-Madelung indole synthesis to other activated benzylic systems as shown in Scheme 6 (equations 1-3) [17]. These include phenylsulfonyl, thiomethyl, and cyano, and this team applied this chemistry to a synthesis of the alkaloid isocryp-tolepine. As we saw twice in the previous chapter, the cycli-zation of phosphonium salt 15 affords quinolone 16, which was used to synthesize both neocryptolepine (17) and isocryptolepine (18). 

Scheme 2 Applications of the Wittig-Madelung Indole Synthesis...

Hughes developed a polymer-bound phosphonium salt support for a solid phase Wittig-Madelung indole synthesis (Scheme 8) [21]. The method uses a commercially available polymer-bound triphenylphosphine 22. 

Intramolecular Wittig-type cyclizations have been used successfully in many ring-synthesis applications, and some further examples reported this year include the preparation of chromones by cyclization of the carbonate (149) and an indole synthesis from O-acyl benzyltriphenylphosphonium salts. The bicyclo[3.3.0]oct-A -en-3-one ring system lacking substituents at C-2 and C-5 is produced by ring closure of the phosphonates (150), although in the case of the parent member of the series (150, R = R = H) a novel dimer is formed... 

Beckmann rearrangement, 4, 292 pyrolysis, 4, 202 synthesis, 4, 223 Wittig reaction, 4, 294 Wolff-Kishner reduction, 4, 291 Indole, 1-acyl-2,3-disubstituted photoisomerization, 4, 204 photo-Fries rearrangement, 4, 204 photoisomerization, 4, 42 synthesis, 4, 82 Indole, 2-acyl acidity, 4, 297 synthesis, 4, 337, 360 Indole, 3-acyl-acidity, 4, 297 cleavage, 4, 289 reduction, 4, 289 synthesis, 4, 360 Indole, 7-acyl-synthesis, 4, 246... 

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