ISSN:
0894-3230
Keywords:
Organic Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
,
Physics
Notes:
In many reactions of magnesium reagents, including Grignard and aryliminodimagnesium [ArN(MgBr)2, IDMg], the formation of abnormal products via reactions such as radical dimerization, hydrogen abstraction and conjugate 1,4-addition orginating from efficient single electron transfer (SET) is not excluded. In IDMg reactions with benzonitrile and N,N-dimethylformamide in tetrahydrofuran, however, clean reactions took place affording N-arylbenzamidine and N,N′-diarylformamidine via exclusive 1,2-addition and condensation plus replacement, respectively. Some alkyl and arylvinyl cyanides gave the corresponding amidines without 1,4-addition or hydrogen abstraction. These results are the first observation of such reactions of magnesium reagents, and are attributed to a combination of the weak electron-donating ability (EDA) of IDMg with the weak electron-accepting ability (EAA) of nitriles. Although ESR is therefore inapplicable, factors governing the product yields were studied on the basis of effects caused by the addition of strongly coordinating hexamethylphosphoramide and pyridine to the reagent solution, and by addition of nitrobenzenes having a strong EAA. From the results, a large participation of σ-complexation followed by implicit SET in the inner sphere of the complex is proposed.
Additional Material:
6 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/poc.610060905
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