Trapping phosphodiester-quinone methide adducts through in situ lactonization

The goal of in situ modification of DNA via phosphodiester alkylation has led to our design of quinone methide derivatives capable of alkylating dialkyl phosphates. A series of catechol derivatives were investigated to trap the phosphodiester-quinone methide alkylation adduct through in situ lactonization. The catechol derivatives were uniquely capable of characterizable p-quinone methide formation for mechanistic clarity. These investigations revealed that with a highly reactive lactonization group (phenyl ester), lactonization competed with quinone methide formation. Lactone-forming groups of lower reactivity (methyl ester, n-propyl ester, and dimethyl amide) allowed quinone methide formation followed by phosphodiester alkylation; however, they were ineffective at in situ lactonization to drain the phosphodiester alkylation equilibrium to the desired phosphotriester product. The derivatives tethered with lactone-forming functionality of intermediate reactivity (chloro-, trichloro-, and trifluoroethyl esters), allowed quinone methide formation, phosphodiester alkylation, and in situ lactonization to efficiently afford the trapped phosphotriester adduct.     

Bromination of sydnones. I. Reaction with 3-arylsydnones containing electron-donors on the aryl ring

Bromination has been examined for a series of 3-arylsydnones (1) with electron donors (dimethyl to dimethoxy) on the aryl ring. In no example was exclusive aryl ring bromination observed, however, exclusive sydnone ring bromination could be realized in every case. For two dimethoxyphenyl examples both aryl and sydnone ring bromination occurred.     

Synthèse du mèthyl-1 diformyl-2,3 pyrrole,de la méthyl-1 pyrrolo[2,3-d] pyridazine et de la méthyl-1 oxo-6 (6h)cycloheptatrieno[b] pyrrole

This communication describes the synthesis of l-methyl-2,3-diformylpyrrole. This new compound is used to prepare a new heterocycle, l-methylcyclohepta[b]pyrrol-6-one and thus allows a new synthesis of l-methylpyrrolo[2,3-d]pyridazine.     

Dearomatising rearrangements of lithiated thiophenecarboxamides

Thiophene-3-carboxamides bearing allyl or benzyl substituents at nitrogen undergo dearomatising cyclisation on treatment with LDA. Rearrangements transform the dearomatised products into pyrrolinones, azepinones or partially saturated azepinothiophenes.     

Magnetic exchange interactions in tetrabromocuprate compounds

Magnetic and structural data for 28 compounds containing the tetrabromocuprate ion are presented. The parameters which affect the strength and sign of the magnetic superexchange interaction via non-bonding contacts between bromide ions are described and a system for describing the topology of the interaction between tetrahedra is proposed. Analysis of the data suggests that the primary factors affecting the magnetic exchange are the Br?Br distance, the Cu-Br?Br angle and the Cu-Br?Br-Cu dihedral angle.     

Methodology for the synthesis of the core EFGH rings of diazonamide A

Conversion of substituted 2-oxindoles into 2-thionoindoles followed by Raney nickel desulfurization provides a mild method for synthesizing the core EFGH rings of diazonamide A.