Gold chiral

Bartolome C, Garcia-Cuadrado D, Ramiro Z, Espinet P. Synthesis and catalytic activity of gold chiral nitrogen acycHc carbenes and gold hydrogen bonded heterocyclic carbenes in cyclopropanation of vinyl arenes and in intramolecular hydroalkoxylation of allenes. Inorg Chem. 2010 49 9758-9764. 

Togni A., Pastor S. D. Cooperativity of Chirality in Homogeneous Catalysis The Gold(I)-Catalyzed Aldol Reaction and the Vanadium(IV)-Catalyzed Hetero-Diels-Alder Cycloaddition Chirality 1991 3 331-340... 

As indicated above in chiral mesophases, the introduction of a functional group in mesogenic stmctures offers the opportunity to achieve functional LCs. With this aim, mesomorphic crown-ether-isocyanide-gold(I) complexes (26) have been prepared recently [38]. The derivatives with one alkoxy chain show monotropic SmC mesophases at or close to room temperature. In contrast, the complexes with three alkoxy chains behave as monotropic (n = 4) or enantiotropic (n > 4) LCs. The structure of the mesophases could not be fully eluddated because X-ray diffraction studies in the mesophase were unsuccessful and mesophase characterization was made only on the basis of polarized optical microscopy. These complexes are luminescent not only in the solid state and in solution, but also in the mesophase and in the isotropic liquid state at moderate temperatures. The emission spectra of 26a with n=12 were... 

Mixtures of a nematic liquid crystal (LC or LC ) with small quantities of gold nanoparticles coated with alkylthiolates (<5 wt%) including an alkylthiolate functionalized with a chiral group have been studied (Figure 8.29) [72]. All mixtures show nematic mesophases with transition temperatures and phase stability very similar to those oftheliquid crystal precursors LC or LC. The introduction ofachiral center into the mixtures (mixtures of Au ) produce chiral nematic mesophases. A similar result is obtained in mixtures of Au and LC doped with the chiral dopant (s)-Naproxen. 

Omenat, A., Serrano, J.L., Sierra, T., Amabilino, D.B., Minguet, M., Ramos, E. and Veciana, J. (1999) Chiral linear isocyanide palladium(II) and gold(I) complexes as ferroelectric liquid crystals. Journal of Materials Chemistry, 9, 2301-2305. 

Circular dichroism (CD) is another interesting example of an optical property of the small Au SR clusters. Since the first observation of Schaaff et al. [23,24], several reports have appeared regarding the CD activities of gold clusters protected by chiral thiols such as penicillamine [25] and A-isobutyryl-cysteine [26]. Figure 11 shows the CD spectra of 1-9, which is a good reproduction of the original report by Whetten s group [23,24]. 

The Au SG clusters were optically active in the visible and UV spectral range, with the anisotropy factors in the order of several tens to hundred parts per million. The origin of the observed optical activity in core-based electronic transitions has been previously discussed [24]. The key question is whether the gold cluster is intrinsically chiral or whether the optical activity is induced by the chiral ligation environment. The first possibility has been supported by theoretical studies performed by Garzon and... 

The gold(I) complex of a chiral ferrocenylphosphine complex promotes asymmetric aldol reactions of a-isocyanocarboxylates to form chiral oxazolines in high diastereo- and enantio-selectivities (Scheme 52).225,226 In these reactions, the analogous silver(I) ferrocenylphosphine complex also works well. 

The first gold catalyzed C-S bond formation was demonstrated in a route to the 2,5-dihydrothiophene 16 via cycloisomerization of the allene 17 which occurred with high chirality transfer (d.r. > 95 5) <06AG(E)1897>. 

Ray SG, Daube SS, Leitus G, Vager Z, Naaman R (2006) Chirality-induced spin-selective properties of self-assembled monolayers of DNA on gold. Phys Rev Lett 96(3) 036101... 

Intermolecular addition of activated methylenes to unsaturated systems has been investigated with silver,36 silver/ gold, and palladium catalysts. Thus, C-H addition of 2,4-pentandione to 1,3-cyclohexadiene occurs in THF at 0°C with 5mol% of palladium(ll) catalyst without base. Josiphos ligand 20 is used as a chirality source to induce... 

Asymmetric Aldol Reactions with a Chiral Ferrocenylphosphine-Gold( I) Complex... 

Asymmetric aldol reaction. In the presence of a gold(I) complex (1) and a chiral ferrocenylphosphine (2), various aldehydes react with methyl isocyanoacetate... 

The Diels-Alder reaction outlined above is a typical example of the utilization of axially chiral allenes, accessible through 1,6-addition or other methods, to generate selectively new stereogenic centers. This transfer of chirality is also possible via in-termolecular Diels-Alder reactions of vinylallenes [57], aldol reactions of allenyl eno-lates [19f] and Ireland-Claisen rearrangements of silyl allenylketene acetals [58]. Furthermore, it has been utilized recently in the diastereoselective oxidation of titanium allenyl enolates (formed by deprotonation of /3-allenecarboxylates of type 65 and transmetalation with titanocene dichloride) with dimethyl dioxirane (DMDO) [25, 59] and in subsequent acid- or gold-catalyzed cycloisomerization reactions of a-hydroxyallenes into 2,5-dihydrofurans (cf. Chapter 15) [25, 59, 60],... 

Figure 16. Structure of chiral Co(salen) 48 immobilized on gold colloids.

Hie first helical SmC mesophase for a gold(I) mesogen has been prepared by means of complexation to an enantiomerically pure chiral isocyanide (Figure 7.32) [30]. This... 

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