Replacing the Z-phenyl Ring in Tamoxifen® with a para-Connected NCN Pincer-Pt-Cl Grouping by Post-Modification

Post-modification of a series of NCN-pincer platinum(II) complexes [PtX(NCN-R-4)] (NCN = [C6H2(CH2NMe2)2-2,6]–, R = C(O)H, C(O)Me and C(O)Et), X = Cl– or Br–) at the para-position using the McMurry reaction was studied. The synthetic route towards two new [PtCl(NCN-R-4)] (R = C(O)Me and C(O)Et) complexes used above is likewise described. The utility and limitations of the McMurry reaction involving these pincer complexes was systematically evaluated. The predicted “homo-coupling” reaction of [PtBr(NCN-C(O)H-4)] led to the unexpected formation of 3,3′,5,5′-tetra[(dimethylamino)methyl]-4,4′-bis(platinum halide)-benzophenone (halide = Br or Cl), referred to hereafter as the bispincer-benzophenone complex 13. This material was further characterized using X-ray crystal structure determination. The applicability of the pincer complexes in the McMurry reaction is shown to open a route towards the synthesis of tamoxifen-type derivatives of which one phenyl ring of Tamoxifen® itself is replaced by an NCN arylplatinum pincer fragment. The newly synthesized derivatives can be used as potential candidates in anti-cancer drug screening protocols. Two NCN-arylpincer platinum tamoxifen type derivatives, 5 and 6, were successfully synthesized and of 5 the separation of the diastereomeric E-/Z-forms was achieved. Compound 6, which is the pivaloyl protected NCN pincer platinum hydroxy-Tamoxifen® derivative, was obtained as a mixture of E-/Z-isomers. The new derivatives were further analyzed and characterized with 1H-, 13C{1H}- and 195Pt{1H}-NMR, IR, exact mass MS and elemental analysis.

Photoinitiated carbonyl-metathesis: deoxygenative reductive olefination of aromatic aldehydes via photoredox catalysis

Carbonyl–carbonyl olefination, known as McMurry reaction, represents a powerful strategy for the construction of olefins.

A cyclopenta[hi]acephenanthrylene bearing two benzoannelated [3.3.3]propellane units: extension of triptindane chemistry

The McMurry reaction of triptindan-9-one (2), a three-fold benzoannelated Cs-symmetrical [3.3.3]propellane ketone, gave trans-9,9′-bitriptindanylidene (5), a sterically crowded stilbene hydrocarbon bearing two E-oriented triptindane moieties, in good yield. Photoisomerization of 5 generated the corresponding cis-stilbene 8 in a photostationary E:Z mixture (55:45), which adopts a similarly crowded C2-symmetrical conformation that is apparently static on the NMR timescale. Photocyclodehydrogenation of 5 via 8 in benzene solution afforded the title hydrocarbon 6, a 1,2,9,10-tetrahydrocyclopenta[hi]acephenanthrylene merged with two triptindane units, in 85% yield. X-ray structure analysis of 6 revealed an essentially planar phenanthrene unit but significant steric repulsion between the pairs of opposite methylene groups of the [3.3.3]propellane cores, giving rise to a C2-symmetrical conformation. Reaction of 2 under modified McMurry conditions (DME instead of THF as a solvent) gave the saturated dimer, 9,9′-bitriptindanyl 7, as a mixture of diastereomers. Attempts to synthesize “columnene” (4), an elusive barrelene derivative fused with two triptindane caps, by three-fold McMurry reaction of triptindane-9,10,11-trione (3) failed.

Anti-proliferative activities of flavone–estradiol Stille-coupling adducts and of indanone-based compounds obtained by SnCl4/Zn-catalysed McMurry cross-coupling reactions

Flavone–estradiol adducts and indanophen based tamoxifen analogs are synthesized using SnCl4–Zn reagent via McMurry reaction and evaluated in human cervical (HeLa) and breast cancer cells (MCF-7 and MDA-MB-231) for the anti-proliferative activity.

Study of Dithienylcyclopentene with Substituents at 4-Position of Thiophene

1-(2,5-Dimethylthien-3-yl)-2-(4-acetyl-2,5-dimethylthien-3-yl) cyclopentene has been synthesized by a six-step procedure, such as Vilsmeier reaction, Wolff-Kishner-Huang reduction reaction, The Friedel-Crafts acylation, McMurry reaction etc. Upon alternate irradiation with 297 and 500 nm light upon 1-(2,5-Dimethylthien-3-yl)-2-(4-acetyl-2,5-dimethylthien-3-yl) cyclopentene, the absorption spectrum changes reversibly and a clear isosbestic point appears. These results suggest that the compound can undergo photochromism and do not decompose during the irradiation.