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A diastereomerically enriched analogue of 1,3,5-triaza-7-phosphaadamantane (PTA) are obtained by reaction of PTA lithium salt with benzaldehyde. The corresponding sulfide [PZA(S)] and crystal structure of oxide [PZA(O)] are synthesized together with an iridium complex.

For knowledge elicitation in contexts where human operators are highly experienced, there are two established protocols available – concurrent and retrospective verbalisations. A third protocol – ‘conspective’ verbalisation – and a synthesised method called collegial verbalisation (CV) which combines the three protocols are presented. Where domain knowledge is shared between colleagues, one might find that they share cognitive strategies. Independent observers (colleagues) comment in the form of conspective protocols on the behaviour of target users. It solves some of the problems associated with the established verbalisation protocols. Three previously published field studies are summarised to illustrate the development of the protocol and the method, provide empirical support, and exemplify the practical value. Based on these studies, a theoretical model is presented. Conspective verbalisation is intended for use in conjunction with concurrent and retrospective verbalisations. Contributing an independent source of data is seen as the major implication of the CV method. [ABSTRACT FROM AUTHOR]

Reaction of (1,3,5-triaza-7-phosphaadamantane-6-yl)lithium (1; PTA-Li), synthesized in high yield and purity, with p-(dimethylamino)benzaldehyde gave the novel water-soluble β-phosphino alcohol (4′-(dimethylamino)phenyl)(1,3,5-triaza-7-phosphatricyclo[3.3.1.1]dec-6-yl)methanol (2; PZA-NMe2). The oxide OPZA-NMe2 (3) and sulfide SPZA-NMe2 (4) were also obtained. Ir(I) complexes of (SR,RS)-PZA-NMe2 and the analogue phenyl(1,3,5-triaza-7-phosphatricyclo[3.3.1.1]dec-6-yl)methanol (PZA) were obtained and used as precatalysts for the hydrogenation of α,β-unsaturated aldehydes and ketones and acetophenone using different mild reduction protocols. The X-ray crystal structure of the SR,RS diastereoisomer of PZA-NMe2 was also obtained and is described herein. [ABSTRACT FROM AUTHOR]

A diastereomerically enriched analogue of 1,3,5-triaza-7-phosphaadamantane (PTA) was obtained by the reaction of PTA lithium salt with benzaldehyde to give the water-soluble derivative phenyl-(1,3,5-triaza-7-phosphatricyclo[3.3.113,7]dec-6-yl)methanol (PZA, 1) as a mixture of two diastereoisomers. PZA derivatives phenyl-(1 ,3,5-triaza-7-phospha-tricyclo[3.3.113,7]dec-6-yl)methanol sulfide [PZA(S), 2] and oxide [PZA(O), 3] were also synthesized. The latter was isolated in the solid state, and the X-ray crystal structure of a single diastereoisomer was obtained. Compound 1 was used as a k1-P monodentate ligand toward iridium(lll) moieties, and the piano-stool complex [Cp*lrCl2(PZA)] (4) was obtained as a mixture of diastereoisomers both in solution and in the solid state. [ABSTRACT FROM AUTHOR]

A series of organometallic compounds of general formula [(arene)M(PTA)(n)X(m)]Y (arene = eta(6)-C(10)H(14), eta-C(5)Me(5)); M = Ru(ii), Os(ii), Rh(iii) and Ir(iii); X = Cl, mPTA; Y = OTf, PF(6)) have been screened for their cytotoxicity and ability to inhibit cathepsin B in vitro, in comparison to the antimetastatic compound NAMI-A. The Ru and Os analogues and NAMI-A showed similar enzyme inhibition properties (with IC(50) values in the low muM range), whereas the Rh(iii) and Ir(iii) compounds were inactive. In order to build up a rational for the observed differences, DFT calculations of the metal complexes adducts with N-acetyl-l-cysteine-N'-methylamide, a mimic for the Cys residue in the cathepsin B active site, were performed to provide insights into binding thermodynamics in solution. Initial structure-activity relationships have been defined with the calculated binding energies of the M-S bonds correlating well with the observed inhibition properties of the compounds.

A diastereomerically enriched analogue of 1,3,5-triaza-7-phosphaadamantane (PTA) was obtained by the reaction of PTA lithium salt with benzaldehyde to give the water-soluble derivative phenyl(1,3,5-triaza-7-phosphatricyclo[3.3.1.13,7]dec-6-yl)methanol (PZA, 1) as a mixture of two diastereoisomers. PZA derivatives phenyl(1,3,5-triaza-7-phospha-tricyclo[3.3.1.13,7]dec-6-yl)methanol sulfide [PZA(S), 2] and oxide [PZA(O), 3] were also synthesized. The latter was isolated in the solid state, and the X-ray crystal structure of a single diastereoisomer was obtained. Compound 1 was used as a k1-P monodentate ligand toward iridium(III) moieties, and the piano-stool complex [Cp*IrCl2(PZA)] (4) was obtained as a mixture of diastereoisomers both in solution and in the solid state.