Aliphatic aldehydes were reacted with nitro alkanes in the presence of catalytic amounts of piperidine over 4 A molecular sieves. Simply by changing reaction conditions (solvent and temperature) it is possible to control the stereochemical outcome of the reactions, obtaining pure (E)- and (Z)-nitro alkenes in high to excellent yields. The role of molecular sieves on the stereochemical control seems crucial in addition to that of piperidine, especially for the synthesis of the Z isomer.
Complexes [Pt(mu-N,S-8-TT)(PPh(3))(2)](2) (1), [Pt(mu-S,N-8-TT)(PTA)(2)](2) (2), [Pt(8-TTH)(terpy)]BF(4) (3), cis-[PtCl(8-MTT)(PPh(3))(2)] (4), cis-[Pt(8-MTT)(2)(PPh(3))(2)] (5), cis-[Pt(8-MTT)(8-TTH)(PPh(3))(2)] (6), cis-[PtCl(8-MTT)(PTA)(2)] (7), cis-[Pt(8-MTT)(2)(PTA)(2)] (8), and trans-[Pt(8-MTT)(2)(py)(2)] (9) (8-TTH(2) = 8-thiotheophylline; 8-MTTH = 8-(methylthio)theophylline; PTA = 1,3,5-triaza-7-phosphaadamantane) are presented and studied by IR and multinuclear ((1)H, (31)P[(1)H]) NMR spectroscopy. The solid-state structure of 4 and 9 has been authenticated by X-ray crystallography. Growth inhibition of the cancer cells T2 and SKOV3 induced by the above new thiopurine platinum complexes has been investigated. The activity shown by complexes 4 and 9 was comparable with cisplatin on T2. Remarkably, 4 and 9 displayed also a valuable activity on cisplatin-resistant SKOV3 cancer cells.
The bisaziridination reaction of symmetric (E-s-trans-E)-α-diimines using ethyl nosyloxycarbamate as aminating agent yields symmetrically functionalized bidiaziridines, under mild conditions. The reactions take place with very high stereoselectivity giving only bidiaziridines with total retention of the starting α-diimine configuration, as determined by NMR measurements. Moreover, only a single pure diastereomer, derived from attack of the aza-anion on the opposite faces of conjugate system was obtained, starting from chiral substrates. ROESY analyses clearly show that all nitrogens have a stable pyramidal conformation, and the absolute configurations of new chiral centers were assigned.
Efficient one-pot methods for the synthesis of variously functionalised conjugated nitro alkenes have been reported. Despite the utility in different fields of these compounds, only a few multi-step syntheses have been reported in the literature, giving the target compounds in low overall yields. α-Nitro acrylates or cinnamates, α-nitro α,β-unsaturated ketones and, most importantly, aromatic and heteroaromatic (E)- 2-nitro allylic alcohols, compounds characterised by a well-known anticancer activity, were obtained in high yields and high diastereomeric purity by a domino condensation-dehydration process.
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