Chirality-driven self-assembly: application toward renewable/exchangeable resin-immobilized catalysts.

Resin-immobilized catalysts were prepared through chirality-driven self-assembly. The method allows the resin-immobilized catalyst to be regenerated under mild conditions and in situ catalyst exchange to be carried out quantitatively. The uniqueness of the methodology was demonstrated by the preparation of a catalyst for TEMPO oxidation as well as a two-step sequential TEMPO oxidation/aldol condensation sequence enabled by facile catalyst exchange.

Construction of Janus dendrimers through a self-assembly approach involving chiral discrimination at a focal point.

A strategy to build Janus dendrimers via the chirality-directed self-assembly of heteroleptic Zn(ii) BOX complexes is reported. The method allows quantitative synthesis of Janus dendrimers in situ without the need for purifications. Each dendritic domain of the Janus dendrimers can be recycled upon disassembly at the focal point.

Efficient generation of perfluoroalkyl radicals from sodium perfluoroalkanesulfinates and a hypervalent iodine(iii) reagent: mild, metal-free synthesis of perfluoroalkylated organic molecules.

This article describes an efficient method for the introduction of perfluoroalkyl groups into N-acrylamides, 2-isocyanides, olefins, and other heterocycles using perfluoroalkyl radicals that were generated from the reaction between sodium perfluoroalkanesulfinates and a hypervalent iodine(iii) reagent. This approach represents a simple, scalable perfluoroalkylation method under mild and metal-free conditions.

Efficient photolytic C-H bond functionalization of alkylbenzene with hypervalent iodine(iii) reagent.

A practical approach to radical C-H bond functionalization by the photolysis of a hypervalent iodine(iii) reagent is presented. The photolysis of [bis(trifluoroacetoxy)iodo]benzene (PIFA) leads to the generation of trifluoroacetoxy radicals, which allows the smooth transformation of various alkylbenzenes to the corresponding benzyl ester compounds under mild reaction conditions.

Mechanism of Metal-Free C-H Activation of Branched Aldehydes and Acylation of Alkenes Using Hypervalent Iodine Compound: A Theoretical Study.

The mechanism of the C-H activation of aldehydes and the succeeding acylation of an alkene using a hypervalent iodine reagent is investigated by theoretical calculations. In contrast to the initial proposed mechanism, the present calculations show that the hypervalent iodine is the initiator of the radical reaction. The formation of acyl radical is rate-determining, and the resulting radical acts as the chain carrier. The kinetic isotope effect (KIE) of deuterated aldehyde, as well as other experimental observations, can now be rationalized from the newly proposed mechanism.

Positive Effect of Water in Asymmetric Direct Aldol Reactions with Primary Amine Organocatalyst: Experimental and Computational Studies.

The origin of higher reactivity in water-accelerated asymmetric aldol reactions with our designed primary amine organocatalyst was elucidated by both computational and experimental methods. As suggested by the calculated transition-state structures for water-promoted imine-enamine isomerization, anti-selective aldol reaction and hemiaminal formation, the rate of this aldol reaction was found experimentally to be even more accelerated by the addition of cis-2-butene-1,4-diol as additive.

Metal-free C-H bond activation of branched aldehydes with a hypervalent iodine(III) catalyst under visible-light photolysis: successful trapping with electron-deficient olefins.

Direct acyl radical formation of linear aldehydes (RCH2-CHO) and subsequent hydroacylation with electron-deficient olefins can be effected with various types of metal and nonmetal catalysts/reagents. In marked contrast, however, no successful reports on the use of branched aldehydes have been made thus far because of their strong tendency of generating alkyl radicals through the facile decarbonylation of acyl radicals. Here, use of a hypervalent iodine(III) catalyst under visible light photolysis allows a mild way of generating acyl radicals from various branched aldehydes, thereby giving the corresponding hydroacylated products almost exclusively. Another characteristic feature of this approach is the catalytic use of hypervalent iodine(III) reagent, which is a rare example on the generation of radicals in hypervalent iodine chemistry.

Two-stage optimization of a supramolecular catalyst for catalytic asymmetric hydroboration.

Systematic changes, first to the structure of the catalyst scaffold and then to the ligating groups, are used to fine tune supramolecular catalysts to achieve high regioselectivity (95-98%) and high enantioselectivity (94-97% ee) across a series of meta-substituted styrenes varying in electronic character.

Ligand scaffold optimization of a supramolecular hydrogenation catalyst: Analyzing the influence of key structural subunits on reactivity and selectivity.

Results are reported for the catalytic asymmetric hydrogenation of two prototypical substrates with a series of more than 150 closely related supramolecular catalysts differing in only their ligand/catalyst scaffold. These modular catalysts are constructed from four subunits and vary widely in their reactivity (no reaction to quantitative yield) and enantioselectivity (racemic to 96% ee). Analysis of the ligand/catalyst scaffold optimization data reveals how each subunit contributes to the effectiveness of the modular supramolecular catalyst. The results suggest that a balance between key elements of rigidity and flexibility is required for the successful catalysts and, moreover, that this balance is required to enable effective fine-tuning via catalyst scaffold optimization.

Design of structurally rigid trans-diamine-based Tf-amide organocatalysts with a dihydroanthracene framework for asymmetric conjugate additions of heterosubstituted aldehydes to vinyl sulfones.

Asymmetric conjugate addition of α-heterosubstituted aldehydes such as α-amido and α-alkoxy aldehydes to vinyl sulfone was effected under the influence of structurally rigid trans-diamine-based Tf-amido organocatalyst (S,S)-2 with a dihydroanthracene framework to furnish α,α-dialkyl(amido)aldehydes and α,α-dialkyl(alkoxy)aldehydes with high enantioselectivity. The chiral efficiency of the structurally unique catalyst (S,S)-2 is apparent in comparison with (S,S)-1 and (S,S)-4 with similar functionality.

TADDOL-derived phosphites and phosphoramidites for efficient rhodium-catalyzed asymmetric hydroboration.

[reaction: see text] Two simple TADDOL-derived monodentate ligands, the (1R,2S)-2-phenylcyclohexanol-derived phosphite and the N,N-(phenylbenzyl)phosphoramidite, give comparably high levels of enantioselectivity (90-96% ee) in the rhodium-catalyzed hydroborations of substituted styrenes bearing either electron-donating or electron-withdrawing substituents. Rhodium(I) chloride and tetrafluoroborate catalyst precursors give comparable results. Pinacolborane is superior to catecholborane in these reactions.

Single enantiomer, chiral donor-acceptor metal complexes from bisoxazoline pseudoracemates.

[structure: see text] Single enantiomer, chiral donor-acceptor metal complexes were synthesized via the self-discriminating zinc(II) complexation of a pseudoracemic mixture of donor/acceptor-substituted bisoxazoline derivatives.

Asymmetric catalysis using self-assembled chiral bidentate P,P-ligands.

A strategy is described for modular catalyst development based upon metal-directed self-assembly of bifunctional subunits around a structural metal to form a heteroleptic complex in which a second set of ligating groups are now suitably disposed to bind a second metal to form a catalytic site. A library of chiral diphosphites was prepared via metal-directed self-assembly and used in a simple asymmetric allylic amination, giving enantiomeric excesses as high as 97%.

Functional coupling of capping and transcription of mRNA.

In humans, 5' m(7)G cap addition is accomplished cotranscriptionally by the sequential action of the capping enzyme (Hce1) and the cap methyltransferase (Hcm1). We found that guanylylation and methylation occur efficiently during transcription with t(1/2)'s of less than 15 and 70 s, respectively. A two to four order of magnitude increase was found in the rate of guanylylation of RNA in transcription complexes compared to free RNA. This stimulation required only the RNA polymerase II elongation complex and Hce1. Capping activity was weakly associated with elongation but not preinitiation complexes. The CTD was not required for functional coupling but stimulated the rate of capping 4-fold. Inhibition of Cdk7 but not Cdk9 similarly slowed the rate of capping.