Dihydro- 1H- pyrrolo [1,2-a] indol-1-yl carboxylic derivatives which act as S1P1 agonists
A solvate, C1-C6 technology, used in anti-inflammatory agents, drug combinations, antiviral agents, etc., can solve problems such as β-cell toxicity and discomfort
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[0590] for the active level of 125 The synthetic method that I is combined in the target molecule comprises:
[0591] A. Sandmeyer and similar reactions: This method converts aryl or heteroaryl amines into diazonium salts, such as diazonium tetrafluoroborate, and the subsequent use of Na 125 I convert to 125 I labeled compound. A representative method is reported by Zhu, G-D and colleagues in J. Org. Chem., 2002, 67, 943-948.
[0592] B. The ortho iodine of phenol ( 125 I)ization: This method allows 125 I was bound in the ortho position to the phenol as reported by Collier, T.L and co-workers in J. Labelled Compd. Radiopharm., 1999, 42, S264-S266.
[0593] C. For aryl bromides and heteroaryl bromides 125 I Exchange: The method is usually a two-step process. The first step is to convert the aryl or heteroaryl bromide to the corresponding trialkyltin intermediate using, for example, the following method: 3 ) 3 SnSn(CH 3 ) 3 ] in the presence of Pd-catalyzed reactions ...
Embodiment 1
[0599] Embodiment 1: the synthesis of compound of the present invention
[0600] Exemplary syntheses for compounds of the invention are shown in Figures 7 to 12 , where the symbols have the same definitions as those used throughout this specification.
[0601] The compounds of the present invention and their synthesis are further illustrated by the following examples. The following examples are provided to further define the invention without, however, limiting the invention to the specifics of these examples. Compounds described before and after this application were named according to AutoNom version 2.2 or CS ChemDraw Ultra version 9.0.7. In some instances, common names are used, and it is understood that such common names will be known to those skilled in the art.
[0602] Chemistry: Proton NMR ( 1 H NMR) spectra were recorded on a Bruker Avance-400 equipped with QNP (Quad Nucleus Probe) or BBI (Broad Band Inverse) and z-gradient. Chemical shifts are given in parts p...
Embodiment 11
[0604] Example 1.1: Preparation of 2-(7-(5-(6-cyanopyridin-3-yl)-1,2,4-oxadiazol-3-yl)-2,3-dihydro-1H-pyrrole and[1,2-a]indol-1-yl)acetic acid (compound 3).
[0605] Step A: Preparation of 2-(7-(5-(6-cyanopyridin-3-yl)-1,2,4-oxadiazol-3-yl)-2,3-dihydro-1H-pyrrolo [1,2-a]indol-1-yl) tert-butyl acetate.
[0606] To 2-(7-(N'-hydroxyamidino)-2,3-dihydro-1H-pyrrolo[1,2-a]indol-1-yl)acetic acid tert-butyl ester (50mg, 0.152mmol ) in dioxane (914μl) and 6-cyanonicotinic acid (45.0mg, 0.304mmol), successively add TEA (212μL, 1.518mmol) and 1-propyl phosphoric acid cyclic anhydride (49.2μL, 0.167 mmol). The reaction mixture was stirred for 30 min, heated at reflux for 18 h, then diluted with water. The resulting precipitate was filtered off and washed with water to give the title compound as a yellow solid (43mg). LCMS m / z=442.4[M+H] + .
[0607]Step B: Preparation of 2-(7-(5-(6-cyanopyridin-3-yl)-1,2,4-oxadiazol-3-yl)-2,3-dihydro-1H-pyrrolo [1,2-a]indol-1-yl)acetic acid (compo...
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