Reductively disilylated N-heterocycles as versatile organosilicon reagents.

The reductively disilylated N-heterocyclic systems 1,4-bis(trimethylsilyl)-1-aza-2,5-cyclohexadiene (1Si), 1,4-bis(trimethylsilyl)-1,4-dihydropyrazine (2Si) and its methyl derivatives (3Si and 4Si), and 1,1'-bis(trimethylsilyl)-4,4'-bipyridinylidene (5Si) are proficient organosilicon reagents owing to their low first vertical ionization potentials and the heterophilicity of the polarized N-Si bonds. These have prompted their reactivity as two-electron reductants or reductive silylations. These reactions benefit from the concomitant rearomatization of the N-heterocycles and liberation of trimethylsilyl halides or (Me3Si)2O, which are mostly volatile or easily removable byproducts. In this perspective, we have discussed the utilization of these reductively disilylated N-heterocyclic systems as versatile reagents in the salt-free reduction of transition metals (A) and main-group halides (B), in organic transformations (C) and in materials syntheses (D).

Versatile coordinating abilities of acyclic N4 and N2P2 ligand frameworks in conjunction with Sn[N(SiMe3)2]2.

The adaptability of three acyclic tetradentate ligands with the -CHR-CHR- (R = H or alkyl substituent) linker in the backbone: bis(α-iminopyridine) L1 and the reduced form L2 and diaminodiphosphine L3 to stabilize various stannylenes has been explored. The reaction of L1 with two equivalents of Sn[N(SiMe3)2]2 led to the stabilization of a bisstannylene 1 through the ene-amide transformation of L1. The reaction of bisstannylene 1 with B(C6F5)3 and silver trifluoromethane sulfonate led to the formation of ligand stabilized Sn(ii) dications 2 and 3 respectively. A mixture of Sn(ii) dication 3 and a Sn(ii) monocation 4 has been obtained from the reaction between 1 and trimethylsilyl trifluoromethane sulfonate. A 1 : 1 stoichiometric reaction between L3 and Sn[N(SiMe3)2]2 led to the isolation of a dimeric monostannylene 5 having a step-like structure with a Sn2N2 central ring. The reaction of L2 with Sn[N(SiMe3)2]2 underwent an electron transfer reaction ultimately leading to bis(α-iminopyridine) isolation.

Stabilization of bis(chlorogermyliumylidene)s within bifunctional PNNP ligand frameworks and their reactivity studies.

The diiminodiphosphine (Lim) and diaminodiphosphines (l-NH and l-NMe) with a bifunctional PNNP ligand framework have been employed to host two [GeCl]+ units leading to the formation of bis(chlorogermyliumylidene) 1-3, respectively. The synthetic route involves a 1 : 2 stoichiometric reaction between the PNNP ligand and GeCl2·dioxane and the subsequent addition of two equivalents of chloride abstracting agent. Compound 1 is unstable towards coordinating solvents and Lewis bases, resulting in the displacement of the GeCl unit and the formation of rearranged products 4 and 5. However, the diaminodiphosphine coordinated Ge(ii) bis(monocation)s 2 and 3 proved to be stable and revealed their electrophilic behaviour towards the Lewis bases studied.

Bis(chlorogermyliumylidene) and its significant role in elusive reductive cyclization.

Bis(chlorogermyliumylidene) 2 has been strategically obtained within redox-active bis(α-iminopyridine). Metal-free reduction of 2 followed by protonation led to elusive 2,3-di(pyridin-2-yl)piperazine with meso-stereoselectivity. Formation of persistent triplet diradicals upon reduction and isolation of piperazine stabilized Ge(ii) dication intermediates provide convincing evidence for the crucial role of [GeCl]+ units in reductive cyclization.

Design and synthesis of multifunctional gold nanoparticles bearing tumor-associated glycopeptide antigens as potential cancer vaccines.

The development of vaccines against specific types of cancers will offer new modalities for therapeutic intervention. Here, we describe the synthesis of a novel vaccine construction prepared from spherical gold nanoparticles of 3-5 nm core diameters. The particles were coated with both the tumor-associated glycopeptides antigens containing the cell-surface mucin MUC4 with Thomsen Friedenreich (TF) antigen attached at different sites and a 28-residue peptide from the complement derived protein C3d to act as a B-cell activating "molecular adjuvant". The synthesis entailed solid-phase glycopeptide synthesis, design of appropriate linkers, and attachment chemistry of the various molecules to the particles. Attachment to the gold surface was mediated by a novel thiol-containing 33 atom linker which was further modified to be included as a third "spacer" component in the synthesis of several three-component vaccine platforms. Groups of mice were vaccinated either with one of the nanoplatform constructs or with control particles without antigen coating. Evaluation of sera from the immunized animals in enzyme immunoassays (EIA) against each glycopeptide antigen showed a small but statistically significant immune response with production of both IgM and IgG isotypes. Vaccines with one carbohydrate antigen (B, C, and E) gave more robust responses than the one with two contiguous disaccharides (D), and vaccine E with a TF antigen attached to threonine at the 10th position of the peptide was selected for IgG over IgM suggesting isotype switching. The data suggested that this platform may be a viable delivery system for tumor-associated glycopeptide antigens.