TY - JOUR

T1 - A route to 1,2,4-oxadiazoles and their complexes via platinum-mediated 1,3-dipolar cycloaddition of nitrile oxides to organonitriles

AU - Bokach, Nadezhda A.

AU - Khripoun, Anatolii V.

AU - Kukushkin, Vadim Yu

AU - Haukka, Matti

AU - Pombeiro, Armando J.L.

PY - 2003/2/10

Y1 - 2003/2/10

N2 - A significant activation of the C≡N group in organonitriles upon their coordination to a platinum(IV) center has been found in the reaction of [PtCl4(RCN)2] (R = Me, Et, CH2Ph) with the nitrile oxides 2,4,6-R′3C6H2CNO (R′ = Me, OMe) to give the (1,2,4-oxadiazole)platinum(IV) complexes [PtCl4{N=C(R)ON=CC6H2R′3}] (R = Me, R′ = Me (1); R = Et, R′ = Me (2); R = Et, R′ = OMe (3); R = CH2Ph, R′ = Me (4)); the [2 + 3] cycloaddition was performed under mild conditions (unless poor solubility of [PtCl4(RCN)2] precludes the reaction) starting even from complexed acetonitrile and propionitrile, which exhibit low reactivity in the free state. The reaction between complexes 2-4 and 1 equiv of Ph3P=CHCO2Me in CH2Cl2 leads to the appropriate platinum(II) complexes [PtCl2{N=C(R)-ON=CC6H2R′3}] (5-7); the reduction failed only in the case of 1 insofar as this complex is insoluble in the most common organic solvents. All the platinum compounds were characterized by elemental analyses, FAB mass spectrometry, and IR and 1H, 13C{1H}, and 195Pt NMR spectroscopies, and three of them also by X-ray crystallography. The oxadiazoles formed in the course of the metal-mediated reaction were liberated almost quantitatively from their Pt(IV) complexes by reaction of the latter (complexes 2-4) with an excess of pyridine in chloroform, giving free 1,2,4-oxadiazoles and trans-[PtCl4(pyridine)2]; the sequence of the Pt(IV)-mediated [2 + 3] cycloaddition and the liberation opens up an alternative route for the preparation of this important class of heterocycles.

AB - A significant activation of the C≡N group in organonitriles upon their coordination to a platinum(IV) center has been found in the reaction of [PtCl4(RCN)2] (R = Me, Et, CH2Ph) with the nitrile oxides 2,4,6-R′3C6H2CNO (R′ = Me, OMe) to give the (1,2,4-oxadiazole)platinum(IV) complexes [PtCl4{N=C(R)ON=CC6H2R′3}] (R = Me, R′ = Me (1); R = Et, R′ = Me (2); R = Et, R′ = OMe (3); R = CH2Ph, R′ = Me (4)); the [2 + 3] cycloaddition was performed under mild conditions (unless poor solubility of [PtCl4(RCN)2] precludes the reaction) starting even from complexed acetonitrile and propionitrile, which exhibit low reactivity in the free state. The reaction between complexes 2-4 and 1 equiv of Ph3P=CHCO2Me in CH2Cl2 leads to the appropriate platinum(II) complexes [PtCl2{N=C(R)-ON=CC6H2R′3}] (5-7); the reduction failed only in the case of 1 insofar as this complex is insoluble in the most common organic solvents. All the platinum compounds were characterized by elemental analyses, FAB mass spectrometry, and IR and 1H, 13C{1H}, and 195Pt NMR spectroscopies, and three of them also by X-ray crystallography. The oxadiazoles formed in the course of the metal-mediated reaction were liberated almost quantitatively from their Pt(IV) complexes by reaction of the latter (complexes 2-4) with an excess of pyridine in chloroform, giving free 1,2,4-oxadiazoles and trans-[PtCl4(pyridine)2]; the sequence of the Pt(IV)-mediated [2 + 3] cycloaddition and the liberation opens up an alternative route for the preparation of this important class of heterocycles.

UR - http://www.scopus.com/inward/record.url?scp=0037429202&partnerID=8YFLogxK

U2 - 10.1021/ic026103v

DO - 10.1021/ic026103v

M3 - Article

C2 - 12562205

AN - SCOPUS:0037429202

VL - 42

SP - 896

EP - 903

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 3

ER -