Dual mechanism bifunctional

Figure 1. Chemical structures of the Class I, II, and III dual mechanism bifunctional polymers.

Bifunctional groups were also used to functionalize the St-DVB copolymer. The bifunctional polymers with two different ligands functionalized on the support were synthesized" in order to determine whether synergistic interactions between the ligands could lead to enhanced metal ion affinities and selectivities. These polymers were named dual mechanism bifunctional polymers (DMBPs) (Scheme 11.13)." °... 

Bifunctional Betulinic Acid Derivatives with Dual Mechanisms of Action... 

In conclusion, a "specific role" of these dual "Metal-Support" sites at the metal-support interface has to be considered in addition of the "intrinsic roles" of the metal and the support and a bifunctional mechanism can be reasonably proposed. 

Dual-function catalysts possessing both metallic and acidic sites bring about more complex transformations. Carbocationic cyclization and isomerization as well as reactions characteristic of metals occurring in parallel or in subsequent steps offer new reaction pathways. Alternative reactions may result in the formation of the same products in various multistep pathways. Mechanical mixtures of acidic supports (silica-alumina) and platinum gave results similar to those of platinum supported on acidic alumina.214,215 This indicates that proximity of the active sites is not a requirement for bifunctional catalysis, that is, that the two different functions seem to operate independently. 

The Lewis acid-Lewis base bifunctional catalyst 178a, prepared from Ti(Oi-Pr)4 and diol 174 (1 1), realizes highly enantioselective cyanosilylation of a variety of ketones to (R)-cyanohydrin TMS ethers (Scheme 10.241) [645]. The proposed mechanism involves Ti monocyanide complex 178b as the active catalyst this induces reaction of aldehydes with TMSCN by dual activation. Interestingly, the catalyst prepared from Gd(Oi-Pr)3 and 174 (1 2) serves for exclusive formation of (S)-cyanohy-drin TMS ethers [651]. The catalytic activity of the Gd complex is much higher than that of 178a. The results of NMR and ESI-MS analyses indicate that Gd cyanide complex 179 is the active catalyst. It has been proposed that the two Gd cyanide moieties of 179 play different roles - one activates an aldehyde as a Lewis acid and the other reacts with the aldehyde as a cyanide nucleophile. 

The bifunctional initiator approach using reversible addition fragmentation chain-transfer polymerization (RAFT) as the free-radical controlling mechanism was soon to follow and block copolymers of styrene and caprolactone ensued [58]. In this case, a trithiocarbonate species having a terminal primary hydroxyl group provided the dual initiation (Figure 13.3). The resultant polymer was terminated with a trithiocarbonate reduction of the trithiocarbonate to a thiol allows synthesis of a-hydroxyl-co-thiol polymers which are of particular interest in biopolymer applications. 

Stereo-complex films were reported by Masutani et al7 % combining bifunctional PLLA and PDLA pre-polymers, multi-stereo-block copolymers having different block lengths and sequences are obtained. The resultant copolymers are readily fabricated into transparent films by hot-pressing. The films present excellent thermal stability and thermo-mechanical properties because of the easy formation of stereo-complex crystals. This synthetic method based on tbe dual terminal couplings allows obtaining stereo-block copolymers of PLLA and PDLA showing excellent thermo-mechanical properties and melt processability. 

Zhu, J.-L. Zhang, Y Liu, C. Zheng, A.-M. Wang, W. Insights into the Dual Activation Mechanism Involving Bifunctional Cinchona Alkaloid Thiourea Organocatalysts An NMR and DPT Study. /. Org. Chem. 2012, 77, 9813-9825. 

The dual activation mode of the aforementioned cinchona alkaloid-derived thiourea catalysts proved to be highly effective in catalyzing the asynunetric Mannich reaction, among other transformations. These findings prompted the development of new, more simple bifunctional chiral catalysts that are predominately based on tra 5 -l,2-diaminocy-clohexane. For example, the application of the thiourea catalyst 120, which was developed by Takemoto and coworkers, afforded upon the reaction of Af-Boc-protected imines with diethyl malonate the desired chiral amines in good chemical yields (up to 91%) and enantioselectivities (98% ee) (Scheme 11.23) [81]. The catalytic mechanism presumably involves deprotonation and coordination of the active carbonyl compound by the chiral tertiary amine moiety. The formed enolate then attacks the si-face of the... 

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