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1,3‐Dipolar Cycloadditions of Rhodium(III) Azido Complexes with Alkynes and Nitriles
Author(s) -
de Salinas Sara Martínez,
Díez Josefina,
Gamasa M. Pilar,
Lastra Elena
Publication year - 2017
Publication title -
chemistryselect
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.437
H-Index - 34
ISSN - 2365-6549
DOI - 10.1002/slct.201700673
Subject(s) - cycloaddition , chemistry , regioselectivity , rhodium , medicinal chemistry , reactivity (psychology) , ligand (biochemistry) , bromide , double bond , catalysis , organic chemistry , receptor , medicine , biochemistry , alternative medicine , pathology
The diazido complexes [Rh(η 5 ‐C 5 Me 5 )(N 3 ) 2 (PR 3 )] [PR 3 =iPr 2 PCH 2 CH=CH 2 (ADIP), Ph 2 PCH 2 CH=CH 2 (ADPP), PPh 3 ] react with dipolarophiles through 1,3‐cycloaddition reactions and the reactivity and the regioselectivity of the products depend largely of the ancillary phosphane ligand. Thus the reaction with alkynes led to triazolate complexes and the reaction with nitriles gave tetrazolate complexes. In a different manner, the reaction with fumaronitrile led to triazol complexes through [3+2] cycloaddition reaction of one of the azido groups and the C=C double bond of the fumaronitrile. Interestingly, reaction of the alkoxycarbonyl‐1,2,3‐triazolato complexes with benzyl bromide allow the isolation of the free organic triazoles including the not easily available 2,4‐disubstituted‐1,2,3‐triazole ( N 2 )‐N 3 (CH 2 Ph)C 2 (H)CO 2 Me.