Nitrogen direct route

In most zinc enzymes, the metal is tetrahedrally coordinated by either nitrogen atoms alone or by a combination of nitrogen and oxygen atoms. To model zinc enzymes having the much rarer S-donor environments, a number of approaches have been pursued. The most direct routes to such ligands involve the replacement of one or more... 

The nitrolysis of hexamine is a direct route to the military high explosives 1,3,5-trinitro-1,3,5-triazacyclohexane (RDX) and l,3,5,7-tetranitro-13,5,7-tetraazacyclooctane (HMX). " The direct nitrolysis of hexamine with dinitrogen pentoxide in absolute ifitric acid provides RDX in 57 % yield. RDX prepared by this process is exceptionally pure, but other reagents, like ammonium nitrate-nitric acid-acetic anhydride, give much higher yields, partly because they use ammonium nitrate to supplement for ammonium nitrogen deficiency in the reaction. 

So far, several aforementioned intramolecular strategies have been established that all employ highly activated nitrogen source such as carbamates, sulfamates, amides, or azides to achieve C-H functionalization. Although all of them are powerful techniques for the introduction of nitrogen-based functionalities into aliphatic molecule, these methods are unable to provide a direct route toward tertiary amines, which are crucial structural motifs in numerous alkaloids. Therefore, the development of methods for direct N-H/C-H coupling of secondary amine and unactivated alkanes is highly desirable. 

As you can see, there is a nitrogen right in the exact place where one wants it. That is definitely a step in the right direction. But Strike was not very keen on these intermediates because there was really only one decent way to make them that Strike favored and the ways to make final product out of them were not too hot as well. But a lot of things have changed for Strike in a year s time and there are a lot of new promises for this route. 

Preparative routes to aziridines and 1-azirines are derived from cycloelimination processes in which one, and sometimes two, bonds are formed directly to the nitrogen atom (Scheme 1). For aziridines these include the two intramolecular cyclization pathways involving either nucleophilic displacement by the amine nitrogen (or nitrenium anion) on the /3-carbon (route a) or nucleophilic displacement by a /3-carbanionic centre on the amine nitrogen... 

D. Barraclough, The direct or MIT route for nitrogen immobilization a N mirror image study with leucine and glycine. Soil Biol. Biochem. 29 101 (1997). 

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