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3 protocols using 2 iodobenzonitrile

1

Synthesis of Indolo[2,3-d]benzazepinone Derivatives

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2-Iodobenzonitrile, ethyl-1H-indole-carboxylate and 5-bromo-ethyl-1H-indole-carboxylate were purchased from ABCR. Borane solution (1M in THF), absolute DMF, dimethylaminopyridine, di-tert-butyl-dicarbonate, absolute acetonitrile, palladium(II) acetate, sodium bicarbonate, basic aluminuim oxide, 2-acetylpyridine and 2-formylpyridine were bought from Fisher/Acros Organics. Ethoxy-methylchloride was obtained form TCI. Sodium hydride, phosphorus(V) sulfide, celite, hydrazine monohydrate and methyl iodide were purchased from Sigma Aldrich, while lithium hydroxide monohydrate and triphenylphosphine were from Alfa Aesar. 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide-hydrochloride was purchased from IRIS biotech. Silver(I) carbonate was purchased from Merck. 2-Iodobenzylamine was prepared by a known method.26 (link) The unsubstituted indolo[2,3-d]benzazepinone (A) was prepared by following published protocols.18 (link)–20 The 11-bromo-substituted B was prepared using reported precedures,18 (link)–20 with some modifications, a detailed description of the synthesis of B is given in the Supplementary Information file.
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2

Synthesis of Diverse Pyridyl-Substituted Indole Scaffolds

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5-Nitro-1H-indole-3-carboxaldehyde,
2-iodobenzonitrile, and silver(I) carbonate were purchased from abcr.
1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDCI·HCl)
and trifluoroacetic acid were purchased from IRIS biotech, while palladium
(10%) on activated charcoal, tert-butyl dicarbonate
(Boc2O), palladium(II) acetate, 4-(dimethylamino)pyridine
(DMAP), sodium chlorite, and sulfamic acid were obtained from Sigma-Aldrich.
2-Formylpyridine, absolute dimethylformamide (DMF), tetra-n-butylammonium fluoride (TBAF), 4-toluenesulfonyl chloride, triethylamine,
sodium bicarbonate, magnesium sulfate, and borane solution (1 M in
THF) were bought from Fisher/Acros Organics. Triphenylphosphine, sodium
bicarbonate, and celite were purchased from Alfa Aesar. 2-Iodobenzeneethylamine
was prepared by using a literature protolol.28 (link)Synthesis of the main organic scaffolds b1h3 is described in detail in the Supporting Information. 1H NMR spectra of intermediate species b1, b2, c1–c3, d1–d3, e1–e3, f1–f3, g1–g3, h1, and h2 are shown in Figures S36–S54.
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3

Synthesis of Indolo-Benzazepin Derivatives

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2-Iodobenzonitrile,
indole-3-carboxaldehyde, and 5-bromoindole-3-carboxaldehyde
were purchased from ABCR. Borane solution (1 M in THF), absolute DMF,
4-dimethylaminopyridine (DMAP), di-tert-butyl-dicarbonate
(Boc2O), absolute acetonitrile (ACN), palladium(II) acetate,
sodium bicarbonate, tetrabutylammoinium fluoride (TBAF), basic aluminium
oxide, and 2-formylpyridine were bought from Fisher/Acros Organics.
2-Acetylpyridine was obtained from TCI. Sodium hydride (NaH, 60% dispersion
in mineral oil), copper(II) chloride dihydrate, p-toluenesulfonyl chloride, phosphorus pentasulfide, methanol, DCM,
THF, ethyl acetate (EtOAc), hexane, celite, and hydrazine monohydrate
were purchased from Sigma-Aldrich. EDCI·HCl was obtained from
IRIS biotech, while silver(I) carbonate was purchased from Merck.
2-Iodobenzylamine was prepared by a known method.65 (link) The proligands HL5HL11 and the corresponding
complexes 5–11 were prepared as reported previously,33 (link),39 (link) while 5,12-dihydroindolo[3,2-d]benzazepin-7(6H)-one was synthesized by following a literature protocol.37 (link) Absolute hydrazine was preabsoluted over sodium
hydroxide.
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