Synthesis of 5H-imidazo[2,1-c]pyrrolo[1,2-a][1,4]benzodiazepine

We have synthesized 5H-imidazo[2,1-c]pyrrolo[1,2-a][1,4]benzodiazepine 1 in five steps from 1-(2-amino-methylphenyl) pyrrole 4 . Amidino derivatives 11-12 have also been prepared.     

Experiments in mixed-integer linear programming using pseudo-costs

This paper discusses heuristic branch and bound methods for solving mixed integer linear programming problems. The research presented on here is the follow on to that recorded in [3].After a resumé of the concept of pseudo-costs and estimations, new heuristic rules for generating a tree which make use of pseudo-costs and estimations are presented. Experiments have shown that models having a low percentage of integer variables behave in a radically different way from models with a high percentage of integer variables. The new heuristic rules seem to apply generally to the first type of model.Later, other heuristic rules are presented that are used with models having a high percentage of integer variables and with models having a special structure (models including special ordered sets.)The rules introduced here have been implemented in the IBM Mathematical Programming System Extended/370. They are used to solve large mixed integer linear programming models.Numerical results that permit comparisons to be made among the different rules are provided and discussed.     

Trimethylsilyl-directed 1,3-dipolar cycloaddition reactions in the solid-phase synthesis of 1,2,3-triazoles

[reaction: see text] A regioselective method for the preparation of 1,5-trisubstituted 1H-1,2,3-triazoles via a 1,3-dipolar cycloaddition of 1-trimethylsilylacetylenes with organoazides is described. Immobilization of the azide on REM resin and subsequent cycloaddition afforded a 2 x 2 x 4 x 3 membered 1,5-disubstituted 1H-1,2,3-triazole library with an average purified yield of 68%.     

Facile synthesis of 2-bromo-3-fluorobenzonitrile: an application and study of the halodeboronation of aryl boronic acids

A scaleable synthesis of 2-bromo-3-fluorobenzonitrile via the NaOMe-catalyzed bromodeboronation of 2-cyano-6-fluorophenylboronic acid was developed. The generality of this transformation was demonstrated through the halodeboronation of a series of aryl boronic acids. Both aryl bromides and aryl chlorides were formed in good to excellent yields when the corresponding aryl boronic acid was treated with 1,3-dihalo-5,5-dimethylhydantoin and 5 mol % NaOMe.     

The Photochemical and Thermal Interconversion of Some Cyclopentadienone Dimers

In continuation of previous work on cyclopentadienone dimers [3], thermal and photochemical interconversions of the isomeric diketones 1, 3 , and 5 by skeletal rearrangements have been established to the extent summarized in schemes 2 and 3, and the intramolecular [2+2] cycloaddition 1 → 2 was found to be reversible photochemically.