Fluorine containing cyclopropanes : synthesis of aryl substituted all-cis 1,2,3-trifluorocylopropanes, a facially polar motif

We thank the EPSRC for financial support (GR: EP/R013799/1) and we are grateful to the Chinese Scholarship Council (CSC) for Ph.D Studentship support (ZF).The synthesis of substituted all-cis-1,2,3-trifluorocylopropanes are described for the first time. The three fluorines located on each of the cyclopropyl carbons with a stereochemistry where they are all on the same face of the cyclopropane, imparts a significant polarity to the molecule, and the inherent conformational rigidity and lowering of Log P makes this motif attractive for exploration as a substituent for pharmaceuticals and agrochemicals research.PostprintPeer reviewe

Total synthesis of (±)-aspidospermidine, (±)-aspidofractinine, (±)-limaspermidine, and (±)-vincadifformine via a cascade and common intermediate strategy

D.L.C. thanks EPSRC and GSK for a Ph.D. studentship.A concise strategy for the total synthesis of several Aspidosperma alkaloids is reported. A Suzuki–Miyaura cross-coupling provides access to a 2-vinyl indole that undergoes a Diels–Alder cascade reaction with butyn-2-one to deliver a pyrroloindoline intermediate. This undergoes cascade amidation, reduction, skeletal rearrangement, and intramolecular Michael addition to provide a common intermediate containing the full framework of the Aspidosperma alkaloids. The utility of this intermediate is shown in the synthesis of four different natural products.Publisher PDFPeer reviewe

Fluorinated liquid crystals: evaluation of selectively fluorinated facially polarised cyclohexyl motifs for liquid crystal applications

The authors thank the European Research Council for and Advanced Grant and DO’H acknowledges the Royal Society for a Wolfson Merit Award.This paper explores the synthesis of a series of prototype negative dielectric liquid crystalline (LC) compounds which contain fluorinated cyclohexane motifs. The series are analogues and differ only in that they contain between one to four fluorine atoms. The stereochemistry is such that all of the fluorines/C-F bonds are on one face of the cyclohexane ring. This follows from the recent recognition that cyclohexanes with fluorines orientated in one direction, perpendicular to the ring have a strong molecular dipole, a characteristic that might be an advantage in the design of negative dielectric materials. However it is found that the increased polarity, particularly with two or more oriented C-F bonds, leads to higher melting points and poorer solubility in test matrix formulations, relative to hydrocarbon liquid crystals. This arises due to electrostatic intermolecular interactions between the polarised cyclohexyl and aryl rings. The study highlights that in order to take advantage of these polar cyclohexane motifs for liquid crystal design, appropriate scaffolds are required which are free of aromatic rings and contain peripheral solubilising motifs.PostprintPostprintPeer reviewe

A facile synthesis of Robinson’s NHC-stabilised diborane(4)

Reactions of bis(pinacolato)diboron (B2pin2) with [(IDip)AlH3] (IDip = (HCNDip)2C:, Dip = 2,6-iPr2C6H3) afforded both the new diborane [(IDip)BH2B(pin)] and the known compound [(IDip)BH2BH2(IDip)] in a facile one-pot procedure; the latter reaction is improved by the addition of free IDip. [(IDip)AlH3] transfers both IDip and hydride ligands to the diborane moiety in a halide-free approach. [(IDip)BH2B(pin)] was structurally and spectroscopically characterised and additional spectroscopic data for [(IDip)BH2BH2(IDip)] is reported.Publisher PDFPeer reviewe

Cobalt-catalyzed Wagner–Meerwein rearrangements with concomitant nucleophilic hydrofluorination

The authors acknowledge funding from the Royal Society (University Research Fellowship URF\R1\180017 (CPJ) and associated Enhancement Award RGF\EA\181022 (CPJ and RHH)), and the EaSI-CAT Centre for Doctoral Training (RHH and NM).We report a cobalt-catalyzed Wagner-Meerwein rearrangement of gem-disubstituted allylarenes that generates fluoroalkane products with isolated yields up to 84%. Modification of the counteranion of the N-fluoropyridinium oxidant suggests the substrates undergo nucleophilic fluorination during the reaction. Subjecting the substrates to other known metal-mediated hydrofluorination procedures did not lead to observable 1,2-aryl migration. Thus, indicating the unique ability of these cobalt-catalyzed conditions to generate a sufficiently reactive electrophilic intermediate capable of promoting this Wagner-Meerwein rearrangement.Publisher PDFPeer reviewe

Development and Evaluation of a Borohydride-palladium System for Selective Reduction of the C=C Bond of α,β-unsaturated Carbonyl Compounds

Selective reduction of the carbon-carbon double bond of α,β-unsaturated carbonyl compounds is most commonly and reliably effected using a palladium metal catalyst together with molecular hydrogen from a pressurized tank. Sodium borohydride, like other hydrides, is ordinarily associated with reduction of the more polarized carbonyl of such compounds. However, we have developed an alternative means of employing sodium borohydride in combination with palladium metal to selectively reduce the carbon-carbon double bonds of these compounds. In this survey study, we introduce sodium borohydride as an alternative hydrogen source for such selective, palladium-catalyzed reductions. We also compare the results of this new, heterogeneous borohydride-palladium method with that of traditional palladium-catalyzed hydrogenation. A third method using only sodium borohydride with no palladium is included for comparison.Faculty Sponsor: Dr. David B. Corde

The Photophysical Properties of CdTe/ZnS Core/Shell Quantum Dots

The distinctive fluorescent properties of semiconductor nanocrystal quantum dots (QDs) make them advantageous for use in optoelectronic and biological applications. We report on experiments done to characterize the optical properties and the general photostability of CdTe QDs with varying ZnS shell thicknesses. Steady-state and time-resolved absorption and fluorescence spectroscopy measurements indicate that increasing the ZnS shell thickness results in longer absorption and emission wavelengths, increased quantum yield, and improved photostability.Faculty Sponsor: Dr. James J. Butler and Dr. David Corde

Novel five- and six-membered ring phosphorus-selenium heterocycles from selenation of amido-Schiff bases

Authors are grateful to the University of St Andrews for financial support.Woollins’ reagent, [2,4-bis(phenyl)-1,3-diselenadiphosphetane-2,4-diselenide], serving as a selenating-reductive cycloaddition reagent, reacts with nonconjugated amido-Schiff bases to give the corresponding six-membered 1,3,4-selenadiazoles via a ring-expansion accompanied by an additional selenation/cyclization to the imine bond and C═O group; meanwhile, under the same reaction conditions, the selenation of conjugated amido-Schiff bases leads to a series of fused heterocycles with two five-membered rings. Eight single-crystal X-ray structures confirming the formation of these five- and six-membered heterocycles are discussed.Publisher PDFPeer reviewe

Structural diversity in tetrakis(4-pyridyl)porphyrin supramolecular building blocks

The authors would like to thank the University of Alabama Department of Chemistry and the University of Missouri-Columbia Department of Chemistry for support of this work.In memory of a pioneer in crystal engineering, Prof. Israel Goldberg, we report a series of new framework solids, based on the ligand tetrakis(4–pyridyl)porphyrin (TPyP). Spontaneous reactions of TPyP with seven different metal salts under liquid-liquid diffusion at ambient temperature show that the formation of ionic compounds is preferred to coordination polymers due to increased conformational freedom. Two coordination networks, {(HgI2)2(TPyP)}n·4nCHCl3∙2nTCE (TCE = 1,1,2,2–tetrachloroethane), and {(Ba(μ1,1–NCS)(μ1,1,3–NCS)(H2O)(MeCN))2(TPyP)}n·4nH2O, displayed a new isomeric form of the known [(HgI2)2(TPyP)]∞ polymeric motif, and a two-dimensional honeycomb polymeric motif linked by hydrogen-bonding into a three dimensional moganite (mog) net, respectively. Four protonated porphyrinic salts, [H3TPyP][PF6]3∙0.5TCE, [H2TPyP][I3]2·2MeOH, [H4TPyP][UO2Cl4]2·6MeCN, and [H4TPyP][Th(NO3)6][NO3]2, were observed which hydrogen bond to give one- or two-dimensional networks, or in the case of [H4TPyP][UO2Cl4]2·6MeCN, a discrete dinuclear hydrogen-bonded complex. In one case, a neutral, hydrogen-bonded complex, Ce(NO3)3(MeOH)3(H2O)·TPyP·TCE·H2O, was formed which adopts a three-dimensional, self-penetrated variant of the face-centered cubic (fcc) network. These new structures represent hybrid organic-inorganic crystalline compounds in which the multidentate porphyrin units, having both hydrogen bonding, as well as coordination functionalities, are interlinked through the inorganic connectors into self-assembled three-dimensional architectures. This work shows the relative stability of noncovalently bound vs. coordination networks as well as the effective potential of the TPyP building block to construct supramolecular assemblies in the presence or absence of coordinating ions as linkers.PostprintPeer reviewe

Exploring the scope of tandem palladium and isothiourea relay catalysis for the synthesis of α-amino acid derivatives

Funding: This research was funded by the School of Chemistry, University of St Andrews. A.D.S. thanks the Royal Society for a Wolfson Research Merit Award.The scope and limitations of a tandem N-allylation/[2,3]-rearrangementprotocol are investigated through the incorporation of a variety of functionalgroups within an allylic phosphate precursor. This method uses readilyaccessible N,N-dimethylglycine aryl esters and functionalizedallylic phosphates, forming quaternary ammonium salts in situ in the presence of a palladium catalyst. Subsequentenantioselective [2,3]-sigmatropic rearrangement, promoted by the chiralisothiourea tetramisole, generates α-amino acid derivatives with two contiguousstereocenters. The incorporation of electron withdrawing ester and amide groupsgave the best results, furnishing the desired products in moderate to goodyields (29-70%), with low diastereocontrol (typically 60:40 dr) but highenantioselectivity (up to 90:10 er). These results indicate that substrate-catalystinteractions in the proposed transition state are sensitive to the substitutionpattern of the substrates.Publisher PDFPeer reviewe