Amidines derived from Pt(IV)-mediated nitrile-amino alcohol coupling and their Zn(II)-catalyzed conversion into oxazolines

Anastassiya V Makarycheva-Mikhailova; Vadim Yu Kukushkin; Alexey A Nazarov; Dmitrii A Garnovskii; Armando J L Pombeiro; Matti Haukka; Bernhard K Keppler; Mathea Sophia Galanski

doi:10.1021/ic034070t

Amidines derived from Pt(IV)-mediated nitrile-amino alcohol coupling and their Zn(II)-catalyzed conversion into oxazolines

Inorg Chem. 2003 Apr 21;42(8):2805-13. doi: 10.1021/ic034070t.

Authors

Anastassiya V Makarycheva-Mikhailova¹, Vadim Yu Kukushkin, Alexey A Nazarov, Dmitrii A Garnovskii, Armando J L Pombeiro, Matti Haukka, Bernhard K Keppler, Mathea Sophia Galanski

Affiliation

¹ Department of Chemistry, St. Petersburg State University, 198504 Stary Petergof, Russian Federation, Institute for Inorganic Chemistry, University of Vienna, Währinger Strasse 42, A-1090 Vienna, Austria.

PMID: 12691592
DOI: 10.1021/ic034070t

Abstract

The reaction between the platinum(IV) complex trans-[PtCl(4)(EtCN)(2)] and the amino alcohols NH(2)CH(2)CH(2)OH, NH(2)CH(2)CH(Me)OH-(R)-(-), NH(2)CH(Ph)CH(2)OH-(R)-(-), NH(2)CH(Et)CH(2)OH-(R)-(-), NH(2)CH(Et)CH(2)OH-(S)-(+), and NH(2)CH(Pr(n)())CH(2)OH proceeds rapidly at room temperature in CH(2)Cl(2) to furnish the amidine complexes [PtCl(4)(HN=C(Et)NH(arcraise;)OH)(2)] (1-6) in good yield (70-80%). The related reaction between the platinum(II) complex trans-[PtCl(2)(EtCN)(2)] and monoethanolamine in a molar ratio of 1:2 in CH(2)Cl(2) results in the addition of 4 equiv of NH(2)CH(2)CH(2)OH per mole of complex to give [Pt(HN=C(Et)NHCH(2)CH(2)OH)(2)(NH(2)CH(2)CH(2)OH)(2)](2+) (7). Formulation of 1-6 is based upon satisfactory C, H, N elemental analyses, electrospray mass spectrometry, IR spectroscopy, and (1)H, (13)C((1)H), (15)N, and (195)Pt NMR spectroscopies, while the structures of trans-[PtCl(4)((Z)-NH=C(Et)NHCH(2)CH(2)OH)(2)] (1), trans-[PtCl(4)((Z)-NH=C(Et)NHCH(2)CH(Me)OH-(R)-(-))(2)] (2), and trans-[PtCl(4)((Z)-NH=C(Et)NHCH(Et)CH(2)OH-(R)-(-))(2)] (4) were determined by X-ray single-crystal diffraction. The Z-amidine configuration of the ligands is preserved in CDCl(3) solutions as confirmed by gradient-enhanced (15)N,(1)H-HMQC spectroscopy and NOE experiments. The amidines, formed upon Pt(IV)-mediated nitrile-amino alcohol coupling, were liberated from their platinum(IV) complexes 1, 3, and 4 by reaction with Ph(2)PCH(2)CH(2)PPh(2) (dppe) giving free NH=C(Et)NHCHRCH(2)OH (R = H 8, Et 9, Ph 10), with the substituents R of different types, and dppe oxides; the P-containing species were identified by (31)P((1)H) NMR spectroscopy. NOESY spectroscopy indicates that the liberated amidines retained the same configuration relative to the C=N double bond, i.e., syn-(H,Et)-NH=C(Et)NHCHRCH(2)OH. The liberated hydroxo-functionalized amidines 8-10 were converted into oxazolines (11-13) in the presence of a catalytic amount of ZnCl(2). A similar catalytic effect has also been reached using anhydrous MSO(4) (M = Cu, Co, Cd), CdCl(2), and AlCl(3).