Pyrrolo 6,9-dione

H,3H- Pyrrolo[l, 2-c]oxazole-l, 3-dione, 5,6,7,8-tetrahydro-IR spectra, 6, 978 [2.2](2,5)Pyrrolophane, N-aryl-rearrangements, 4, 209 Pyrrolophanes natural products, 7, 764 synthesis, 7, 771 Pyrrolophanes, N-aryl-synthesis, 7, 774 (2,4)Pyrrolophanes synthesis, 7, 771 Pyrrolo[3,4-c]pyran-4-ones synthesis, 4, 288 Pyrrolopyrans synthesis, 4, 525, 526 Pyrrolopyrazines synthesis, 4, 526 Pyrrolo[l, 2-a]pyrazines synthesis, 4, 516 Pyrrolo[2,3-6]pyrazines Mannich reaction, 4, 504 Vilsmeier reaction, 4, 505 Pyrrolo[3,4-c]pyrazole, 1,3a,6,6a-tetrahydro-structure, 6, 976 synthesis, 6, 1019 Pyrrolopyrazoles synthesis, 5, 164 Pyrrolo[l,2-6]pyrazoles synthesis, 6, 1002, 1006 Pyrrolo[3,4-c]pyrazoles reactions, 6, 1034 synthesis, 6, 989, 1043 Pyrrolo[3,4-c]pyrazolones synthesis, 6, 989 Pyrfolopyridazines synthesis, 4, 517 Pyrrolo[l, 2-6]pyridazines synthesis, 4, 297 6/7-Pyrrolo[2,3-d]pyridazines synthesis, 4, 291 2/f-Pyrrolo[3,4-d]pyridazines synthesis, 4, 291 6/7-Pyrrolo[3,4-d]pyridazines synthesis, 4, 291... 

Pyrrolo[2,3-d]pyrimidine, 5-cyano-bromination, 4, 506 Pyrrolo[2,3-d]pyrimidine, 5-nitroso-nucleophilic reactions, 4, 507 Pyrrolo[l, 2- c]pyrimidine-3-carboxylic acids methyl ester synthesis, 4, 293 Pyrrolopyrimidine-2,4-diones Mannich reaction, 4, 504 Vilsmeier reaction, 4, 505 Pyrrolopyrimidines synthesis, 4, 514, 517, 524, 527 Pyrrolopyrimidines, chloro-nucleophilic attack, S, 312 Pyrrolo[2,3-d]pyrimidines NMR, 4, 500... 

Pyrrolo[3,4-d]thiazole-4,6-dione, 5-ethyl-2-phenylazo-synthesis, 6, 1005 Pyrrolof 1,2-c]thiazoles reactions, 6, 1040 synthesis, 6, 988, 1047 Pyrrolo[2,1 - ijthiazoles synthesis, 6, 293, 992 1 /7,3/7-pyrrolo[l,2-c]thiazoles synthesis, 6, 1006 Pyrrolo[3,2-d]thiazoles synthesis, 6, 1009... 

Phenyl-l//-pyrrolo[3,4-h]quinoxaline-l,3(2//)-dione (589) gave 3-(A(-phenyl-carbamoyl)-2-quinoxalinecarboxylic acid (590, R = H) initially as the crude ammonium salt (590, R = NH4) (NH3, H2O, reflux, 4 h ... 

Benzenesulfonyloxy-1 //-pyrrolo[3,4-/>]quinoxaline-1,3(2F/)-dione (591) gave //-phenyl-3-(A( -phenylureido)-2-quinoxalinecarboxamide (592) (PI1NH2, PhH, 20°C, 6 h 82% the mechanism probably involved Lossen rearrangement at an intermediate stage but remains unprove) A(-p-tolyl-3-(A( -p-tolyl-ureido)-2-quinoxalinecarboxamide (87%) was made similarly using p-toluidine. ... 

Langer and coworkers constructed diverse O- and N-heterocydic scaffolds, such as y-alkylidene-a-hydroxybutenolides and pyrrolo[3,2-b]pyrrol-2,5-diones, exploiting the well-established cyclization strategy of bisnucleophiles with oxalic acid derivatives [163], while Stockman s research group reported in this context on a novel oxime formation/Michael addition providing the structural core of the alkaloid perhydrohistrionicotoxin [164]. 

Thermal decomposition of l,2-dihydro-477-pyrrolo[2,l-r-][l,4]benzoxazine-l,2,4-triones 425 yielded 7-(2,4,6-trimethylbenzoyl)-8-[(2,4,6-trimethylphenoxycarbonyl)-6,10-dihydropyrido[2,l-r-][l,4]benzoxazine-6,10-dione by [4+2] cycloaddition of the initially formed ketene 426 and the subsequent rearrangement of 6,8,9,10-tetrahydropyrido[2,l-c][l,4]benzoxazine-6,8,10-trione 427 (Scheme 36) <1999RCB2131>. 

Thermolysis of 3-alkyloxy- and 3-aroyloxy-5-phenyl-l,2,4-pyrrolo[l,2- ]quinoxaline-l,2,4-triones afforded 5-phenyl-9-(4-phenyl-3-oxo-3,4-dihydro-2-quinoxalinyl)-6,8,10-trioxo-5,6,9,10-tetrahydro-87/-pyrido[l,2-tf ]quinoxaline-7,9-dicarboxylates <2000CHE615, 2004CHE1295> and 7-aroyl-8-aroyloxy-5-phenyl-9-(4-phenyl-3-oxo-3,4-dihydro-2-quinoxalinyl)-5,6-dihydro-1077-pyrido[l,2- ]quinoxaline-6,10-diones <2002CHE498>, respectively. Thermolysis of 3-aryl-2-(5-aryl-2,3-dioxo-2,3-dioxo-4-furanyl)quinoxalines gave 7-aroyl-8-aroyloxy-6-aryl-9-(3-aryl-2-quinoxalyl)-10/7-pyrido[l,2- ]quinoxalin-10-ones <2001CHE1314, 2002RCB850>. 

Reaction of 3-alkylamino-6,8-dimethylpyrimido[4,5-c]pyridazin-5,7-diones 80 with cyclohexyl and cycloheptylamines afforded novel cycloalkano bis(pyrrolo[2,3-c]pyrimido[5,4-e]pyridazines 81 <06T652>. 

Alternatively, pyrrolo[3,4-d]pyrimidine-2,5-diones were synthesized using the same pyrimidine resin precursor, which was first treated with a representative set of primary amines to substitute the chlorine. Subsequent cyclative cleavage was carried out as described previously, leading to the corresponding pyrrolopyrimidine-2,5-dione products in high purity but moderate yield. 

Also in 2001, Azizian described a one-pot diastereoselective synthesis of 2-sub-stituted l,l,2,3,3aa,3b) ,4,5,6,8,8aa-decahydro-8-(spiro-3-indolino-2-one)pyrrolo[3,4-b] pyrrolizine-l,3-dione (151) in good yield and diastereomeric excess using microwave irradiation (Scheme 9.46). 

The pyrrolo[3, 4 2,3]azepino[4,5,6-cd] indole-8,10-dione system can be accessed by reaction, under conditions used for the Pictet-Spengler reaction, of the imines from condensation of 3-amino-4-(3-indolyl) pyrrolin-2,5-diones with aldehydes or ketones. Cyclisation to the pyrrolo-P-carbolines did not occur under the conditions <00JHC1177>. 

Some structures, related to pyrrolo[l,2- ]imidazoles, have been reported. The tricyclic perhydro derivative 49 <1997TL1647> as well as the 3-( 1 //-indol-3-ylmethy 1 )-7a-methyldihydro-1-phenylamino-l//-pyrrolo[ 1,2-tf] imidazole-2,5(3//,6//) dione 50 have been determined and some interesting aspects on compound 50 have been highlighted. 

Table 1 Preparation of various dihydro-1 H-pyrrolo[1,2-a]imidazole-2,5-diones...

Reaction of the thia-amino acid 392 with trifluoroacetic anhydride gave the 2,2,2-trifluoro-l-[7-(trifluoromethyl)-l//-pyrrolo[l,2-c]-[l,3]thiazol-6-yl] ethanone pyrrole 395. The formation of the pyrrole can be rationalized by a sequence involving trifluoroacetylation of the enamine 392 affording dione 393 followed by loss of water and carbon dioxide to give the aromatic product 395. These decarboxylations afford fluorinated derivatives of heterocyclic skeletons known to exhibit interesting biological activity (Scheme 58) <2000T7267>. 

The 3,5-diphenylmorpholine-2-one 161 was used to prepare bicyclic lactams 162 by reaction with the cesium fluoride/tetramethoxysilane system and different Michael acceptors. The adducts were rapidly obtained as a mixture of diastereoisomers that could be separated by column chromatography just after TFA-mediated cyclization to the 8-substituted-4,8a-diphenyltetrahydro-l//-pyrrolo[2,l-r1[l,4]oxazine-l,6(7//)-diones 62 and 163 <1997SL935>. These compounds were then reduced to give substituted prolines as described in Section 11.11.6.1. 

A series of enantiomerically pure tetrahydro-l//-pyrrolo[2,l-c][l,4]oxazine-l,4(3//)-diones 86a-d have been prepared by bromolactonization of acrylamides derived from proline mediated by NBS (Equation 5). These compounds... 

The structures of several compounds containing the pyrrolo[l,2,4]triazine moiety have been established by X-ray crystallography, as for example pyrrolo[l,2- ][l,2,4]triazine 13 <1997J(P1)1829>, 4-acetyl-l-phenyl-2a,3,5-triaza-benz[r-,<7]azulene 14 <2000H(53)323>, heterodiquinane 15 <1998CL1135>, cation 16 derived from methylation of 3-phenylcyclohepta[4,5]pyrrolo[l,2- ][l,3,5]triazine-2,4(377)-dione <2005H(65)1629>, 2-phenyl-3-phenyl-... 

Reaction of /cr/-butyl 1-hydrazinecarboxylates with triphosgene and ethyl 2-pyrrolidinecarboxylate, followed by removal of the BOC-protecting group with gaseous hydrogen chloride in anhydrous acetic acid, yielded hexahydro-pyrrolo[l,2-rf][l,2,4]triazin-l,4-dione 79 (Scheme 9) <2003SC1011>. 

Reduction of all three of the double bonds in the pyrrolo-benzodiazepine-5,11-dione 105 with excess potassium provides the corresponding trans fused hexahydrobenzene derivative 106 in high yield with complete stereochemical control. The preparation of (+)-perhydro-219A 108 from 106 has been reported 3 and a general method of preparation of derivatives of /ra i-2-aminocyclohexanecarboxylic acid e.g. 107) has recently appeared. 

Solid-phase synthesis of a 210 member library of pyrrolo[2,l-c][l,4]benzodiaze-pine-5,ll-diones has been reported (2007JCC29). 

Pyrrolo-benzodiazepine dione 244 can be obtained from the ketoester 243 in refluxing AcOH in high yield (Scheme 52 (1991ZOR1951, 1992CE649, 1996PHA548, 2005H2451)). 

Alkylation of pyrrolo-benzodiazepine dione 244 with methyl iodide occurs on both positions N9 and ClOa, while reaction with 2-bromo diethylaminoethane leads to the low yield of the 4-substituted 248. Acylations with benzoyl and 2-chloroacetyl chlorides are directed exclusively to position 4 to afford 247 (Scheme 52, Section 3.1.1.4 (1992CE649, 2005H2451)). Alkylation of 5H-benzo[/]-pyrrolo[l,2-d][l,4]diazepin-6(7H)-one with a substituted phenethyl bromide has been reported (Scheme 36, Section 3.1.1.1 (1992BMCL1639)). 

The lactam moiety of pyrrolo-benzdiazepine dione 244 can be transformed into the corresponding cyclic imidoyl chloride and further reacted with anilines and aliphatic amines to afford amines 246 (Scheme 52, Section 3.1.1.4 (1996PHA548)). 

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