3- phenyl-1 - indole, procedure

Kozikowski s group has been particularly active in the application of the INOC reaction toward the construction of a variety of natural products. One of the many examples from his laboratory involves the synthesis of tetracyclic compounds possessing suitably functionalized C rings for elaboration to a diverse number of ergot alkaloids via the INOC reaction. A total synthesis of chanoclavine I (65) was accomplished by this chemistry (Scheme 15). The key step in the synthesis involved the conversion of the nitro group of indole (62) into the corresponding nitrile oxide using the phenyl isocyanate procedure developed by Mukaiyama.57 The major product corresponded to isoxazoline (64). The isoxazoline nucleus was converted into chanoclavine I (65) in a series of subsequent steps. The application of nitrile oxide cycloaddition chemistry to the construction of other natural products can be expected to be an active area in future years. 

Reaction Procedure (Scheme 2.92) The Pd-loaded zeolite (0.125 mmol), lithium chloride (0.5 mmol), caesium carbonate (1 mmol), AT-acetyl 2-iodoaniline (0.5 mmol), phenyl acetylene (1.0 mmol), and DMF (10 ml) were added to a sealed tube. The reaction mixture was stirred for 6 h at 140 °C. The reaction mixture was diluted with saturated aqueous ammonium chloride. The product was isolated with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate. The reaction mixture was filtered and concentrated. The product was purified by silica gel column chromatography using hexane-ethyl acetate. 2-Phenyl indole was obtained as a pure product. 

Trp-P-2 (3-amino-l-methyl-5//-pyrido[4,3-h]indole), AaC (2-amino-9//-pyrido[2,3-bJindole), MeAaC (2-amino-3-methyl-9//-pyrido[2,3- ]indole), and PhIP (2-amino-1-methyl-6-phenyl-imidazo[4,5-h]pyridine) and two /3-carbolines comutagens harman (l-methyl-9//-pyrido[4,3-h]indole) and norharman (9//-pyrido[4,3-h]indole). The optimized SPE procedure for isolation and preconcentration comprises the use of diatomaceous earth, propylsulfonyl silica gel, and C18 cartridges to separate selectively the imidazopyridine and indolpyridine derivatives from those of... 

A highly flexible catalytic one-pot procedure for the synthesis of indoles employing or/ o-chloro-substituted l-phenyl-2-alkyl-alkynes or phenyl(aminoalkyl)alkynes as starting materials through a reaction catalyzed by Cp2TiMe2 has been reported.1916... 

General procedure for the one-pot Fischer Indole synthesis To allow comparison of the data, a procedure similar to that described in ref. [5] was used. The catalyst (3.00 g) was suspended into a solution of 1 -phenyl-2-butanone (1.48 g, 10.0 mmoles) in p-xylene (30 g). The mixture was then heated to reflux, and after 15 minutes phenylhydrazine (1.08 g, 10 mmoles) was added in one portion. Samples were taken at regular intervals and analyzed by GC using a CP Sil-5 CB capillary column. In several cases, the indole isomer mixture was isolated from the reaction mixture by vacuum distillation after removal of the catalyst and the solvent. NMR shift values and coupling constants for 4 and 5 were identical to those reported in ref. 

Using a simple ligand-free procedure, Wang et al. prepared the Nl-phenylation product 135 from indole 134 using CUSO4 as the catalyst and K2CO3 as the base [206]. 

Representative procedure for the gold-catalyzed addition of arenes to 1,6-enynes. 3-((l,2,3,6-Tetrahydro-4-methyl-l-tosylpyridin-3-yl)(phenyl)methyl)-lH-indol ... 

Kita s group also described an intermolecular version that resembles the procedure of Engler [8]. This is shown in Scheme 5 and again features phenyliodine(ni) bis(trifluoroacetate) (FIFA) reaction with Al-tosylaniline, followed by nucleophilic attack by an activated olefin, and cyclization to give either Af-tosylindoline (equation 1) or Af-tosylindole (equation 2). The latter is the product when phenyl vinyl sulfides are employed. The thiophenol byproduct was oxidized to diphenyl disulfide with excess FIFA. Four indoles that were prepared in this study are also shown. 

Typical procedure. 2-((S)-hCYano-3-methYlbutYl)-1-(R)-phenyl-1,2,3,4-tetrahYdro-9H-pYr-ido[3,4-b]indole 1414 [1076] A solution of the amide 1413 (0.48 g, 1.33 mmol) and triethylamine (0.4 mL, 2.86 mmol) in dry dichloromethane (50 mL) was cooled to 0 °C and treated with TFAA (0.2 mL, 1.41 mmol). The mixture was allowed to warm to ambient temperature, stirred for 2 h, and then extracted with saturated aq. NaHCOs solution. The organic layer was dried over MgS04 and concentrated in vacuo (bath temperature < 30 °C). Recrystallization of the residue from diethyl... 

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