Enantioselective, Noncovalent, Substrate-Directable Heck-Matsuda and Oxidative Heck Arylations of Unactivated Five-Membered Carbocyclic Olefins.

Highly diastereo- and enantioselective, noncovalent, substrate-directable Heck desymmetrizations of cyclopentenyl olefins containing hydroxymethyl and carboxylate functional groups are presented. These conformationally unbiased cyclic olefins underwent effective arylations in yields of up to 97 %, diastereoselectivity up to >20:1, and enantiomeric excesses of up to 99 %. Noncovalent directing effects were shown to be prevalent in both Heck-Matsuda and oxidative Heck reactions, allowing the preferential formation of cis-substituted aryl cyclopentenes containing two stereocenters, including quaternary stereocenters. These results further validate the internal out-of-coordination-sphere ion-dipole interaction concept directing the reaction diastereoselectivity to the cis-Heck product. This approach is complementary to existing methods using bis-phosphine monoxide ligands to give the opposite trans-diastereoisomer. The applicability of the method is showcased by the straightforward synthesis of a potent phosphodiesterase 4 inhibitor in a diastereo- and enantioselective manner. The reaction is operationally simple and has broad scope with regard to the nature of the arenediazonium salt and boronic acid employed. The mechanism and origin of stereoselectivity were investigated with control experiments and DFT calculations that fully supported the stabilizing internal out-of-coordination-sphere ion-dipole interaction between the resident functional group and cationic palladium.

Enantioselective and Regiodivergent Functionalization of N-Allylcarbamates by Mechanistically Divergent Multicatalysis.

A pair of mechanistically divergent multicatalytic reaction sequences has been developed consisting of nickel-catalyzed isomerization of N-allylcarbamates and subsequent phosphoric-acid-catalyzed enantioselective functionalization of the resulting intermediates. By appropriate selection of reaction partners, in situ generated imines and ene-carbamates are mechanistically partitioned to yield opposing functionalized products. Formal α-functionalization to give protected α-arylamines is achieved upon enantioselective Friedel-Crafts reaction with arene nucleophiles, whereas formal ß-functionalization is achieved upon reaction with diarylimine electrophiles in an enantioselective Povarov-[4+2] cycloaddition.

Enantioselective total synthesis of the highly selective sphingosine-1-receptor VPC01091 by the Heck desymmetrization of a non-activated cyclopentene-fused spiro-pyrrolidinone.

A novel, efficient and enantioselective Heck-Matsuda desymmetrization of non-activated cyclopentene-fused spiro-pyrrolidinones was developed. The reaction provided the Heck products in good to excellent yields and selectivities and tolerated a variety of functional groups in arenediazonium tetrafluoroborates (12 examples) with respect to its electronics and substitution patterns. This methodology was successfully applied in the concise enantioselective total synthesis of VPC01091 (2b), a drug candidate for the treatment of multiple sclerosis.

Photo-assisted inactivation of highly drug resistant bacteria and DPPH scavenging activities of zinc oxide graphted Pd-MCM-41 synthesized by new hydrothermal method.

A major current biomedical challenge is to find materials that are specific, have high efficiency and with long lasting stability to serve as antimicrobial agents. In this contribution we examined new bifunctional nanostructural materials (ZnO/Pd-MCM-41) which were synthesized by a new hydrothermal procedure. To deposit active cites i.e. ZnO, a new protocol was followed in which catechol was used as a precipitating agent. Results indicated that nanostructures comprising palladium nanocrystals of a small size dispersed consistently within the hexagonal pores of the MCM-41 and also ZnO was successfully coated on mesoporous Pd-MCM-41 and that the mesoporous Pd-MCM-41 structure has been well-maintained upon modification of ZnO. The ZnO/Pd-MCM-41 is promising antibacterial agent and have efficient light inhibition activity towards Escherichia coli (E. coli), Psedomonas aeruginosa (P. aeruginosa) and Staphylococcus aureus (S. aureus). The inhibition zone of irradiated ZnO/Pd-MCM-41 nanostructure against E. coli, P. aeruginosa and S. aureus were (17 ± 0.4) mm, 18 (±0.4) mm and 22 (±0.2) mm respectively while that in dark were (9 ± 0.5) mm, 11 (±0.3) mm and 13 (±0.4) mm respectively. The production of reactive oxygen species and hemolytic assay were also analyzed. Different parameters affecting the photo-inhibition efficiency of ZnO/Pd-MCM-41 were also studied. Likewise, the antioxidant activity of these nanostructures was studied against DPPH stabilization. Results indicated that the synthesized nanostructures are highly active and stabilized 99 % DPPH at very low concentration i.e. 1.4 mg/mL.