Stereoselective synthesis of highly substituted tetrahydrofurans by diverted carbene O–H insertion reaction

Copper or rhodium catalyzed reaction of diazocarbonyl compounds with β-hydroxyketones gives highly substituted tetrahydrofurans with excellent diastereoselectivity, under mild conditions, in a single step process that starts as a carbene O–H insertion reaction but is diverted by an intramolecular aldol reaction

Simulating multiple merger pathways to the central kinematics of early-type galaxies

Two-dimensional integral field surveys such as ATLAS^3D are producing rich observational data sets yielding insights into galaxy formation. These new kinematic observations have highlighted the need to understand the evolutionary mechanisms leading to a spectrum of fast-rotators and slow-rotators in early-type galaxies. We address the formation of slow and fast rotators through a series of controlled, comprehensive hydrodynamical simulations sampling idealized galaxy merger scenarios constructed from model spiral galaxies. Idealized and controlled simulations of this sort complement the more 'realistic' cosmological simulations by isolating and analyzing the effects of specific parameters, as we do in this paper. We recreate minor and major binary mergers, binary merger trees with multiple progenitors, and multiple sequential mergers. Within each of these categories of formation history, we correlate progenitor gas fraction, mass ratio, orbital pericenter, orbital ellipticity, and spin with remnant kinematic properties. We create kinematic profiles of these 95 simulations comparable to ATLAS^3D data. By constructing remnant profiles of the projected specific angular momentum (lambda_R = / , triaxiality, and measuring the incidences of kinematic twists and kinematically decoupled cores, we distinguish between varying formation scenarios. We find that binary mergers nearly always form fast rotators. Slow rotators can be formed from zero initial angular momentum configurations and gas-poor mergers, but are not as round as the ATLAS^3D galaxies. Remnants of binary merger trees are triaxial slow rotators. Sequential mergers form round slow rotators that most resemble the ATLAS^3D rotators.Comment: MNRAS, in press, 12 pages, 15 figure

Stereoselective synthesis of highly substituted tetrahydrofurans by diverted carbene O–H insertion reaction

Copper or rhodium catalyzed reaction of diazocarbonyl compounds with β-hydroxyketones gives highly substituted tetrahydrofurans with excellent diastereoselectivity, under mild conditions, in a single step process that starts as a carbene O–H insertion reaction but is diverted by an intramolecular aldol reaction

Total synthesis of the cyclic dodecapeptides wewakazole and wewakazole B

The cyclic dodecapeptides wewakazole and wewakazole B have been synthesized by a divergent strategy via a common tris-proline containing oxazole octapeptide and two separate bisoxazole containing tetrapeptide units, followed by peptide coupling and macrocyclization. The three oxazole amino acid fragments are readily accessible by rhodium(II)-catalysed amide N–H insertion of diazocarbonyl compounds, or by the cycloaddition of rhodium carbenoids with nitriles

Total synthesis of the post-translationally modified polyazole peptide antibiotic plantazolicin A

The power of rhodium carbene methodology in chemistry is demonstrated by the synthesis of a structurally complex polyazole antibiotic. Plantazolicin A, a novel soil bacterium metabolite, comprises a linear array of 10 five-membered rings in two pentacyclic regions that derive from ribosomal peptide synthesis followed by extensive post-translational modification. The compound possesses potent antimicrobial activity, and is selectively active against the anthrax causing organism. A conceptually different synthesis of plantazolicin A is reported in which the key steps are the use of rhodium(II)-catalyzed reactions of diazocarbonyl compounds to generate up to six of the seven oxazole rings of the antibiotic. NMR Spectroscopic studies and molecular modeling, reveal a likely dynamic hairpin conformation with a hinge region around the two isoleucine residues.The compound has modest activity against methicillin-resistant Staphylococcus aureus (MRSA)

Bundling of actin filaments by aorta caldesmon is not related to its regulatory function

AbstractCa2+-sensitive thin filaments from vascular smooth muscle were disassembled into their constituent proteins, actin, tropomyosin and caldesmon. Caldesmon bound to both actin and to actin-tropomyosin and inhibited actin-tropomyosin activation of skeletal muscle myosin MgATPase. It also promoted the aggregation of actin or actin-tropomyosin into parallel aligned bundles. Quantitative electron microscopy measurements showed that with 1.1 μM actin-tropomyosin, 1.6 ± 0.5% (n = 3) of the filaments were in bundles. At 0.073 μM, caldesmon inhibited MgATPase activity by 50%, whereas bundling was 3.0 ± 1.3% (n = 4). At 0.37 μM caldesmon, MgATPase inhibition was 83% while 28.1 ± 6.9% (n = 4) of filaments were in bundles. Experiments at 4.4 μM in which MgATPase and bundling were measured in the same samples gave similar results. Small bundles of 2–3 filaments showed the most frequent occurrence at 1.1 μM actin. At 4.4 μM actin the most common bundle size was 3-5 filaments, with the occasional occurrence of large bundles consisting of up to 120 filaments. The incidence of bundling was the same in the presence and absence of tropomyosin. Thus caldesmon can induce the formation of actin bundles but this property bears no relationship to its inhibition of MgATPase activity

Origin of the thiopyrone CTP-431 “unexpectedly” isolated from the marine sponge Cacospongia mycofijiensis

An intriguing hypothesis that latrunculin A, a well-known natural product, might have undergone transformation into the unprecedented thiopyrone CTP-431 upon long-term storage in methanol is advanced. Thus opening of the hemiacetal of latrunculin A, followed by E1CB elimination, and dehydration would give a polyene that could undergo intramolecular Diels-Alder reaction, followed by methanolysis of the thiazolidinone ring and ring closure by intramolecular thiol addition to an enone. Experimental evidence that the novel thiazolidinone to thiopyrone rearrangement can occur is presented.The marine sponge Cacospongia mycofijiensis, found in the ocean surrounding Fiji, is a source of several polyketide natural products with interesting biological properties,1 including the tubulin binding macrolide fijianolide B (also known as laulimalide),2,3 the HIF1 signal inhibitor mycothiazole,4,5 and the macrolide latrunculins (Figure 1).6 The thiazolidinone-containing latruculins are of mixed polyketide synthesis (PKS) and non-ribosomal peptide synthesis (NRPS) origin, and latrunculin A 1 disrupts microfilament assembly to such an extent that it is the most widely used chemical tool to study actin binding

On the structure and dynamics of stratified wakes generated by submerged propagating objects

The article of record as published may be found at http://dx.doi.org/10.1080/1755876X.2017.1307801The structure and intensity of the intermediate wake generated by a submerged propagating body in a stratified fluid was studied using a combination of (i) numerical simulations, (ii) field measurements, and (iii) laboratory experiments. The numerical component offered guidance for the field work performed in Monterey Bay (CA, USA) in the summer of 2015. The field work focused on subsurface thermal signatures of a submerged propagating object. Vertical temperature profiles suggested that long-term changes in thermal stratification can occur after the passage of a towed body. Horizontal temperature variability, measured by an autonomous underwater vehicle facilitated the identification of the wake using perturbation temperature variance as the key diagnostic variable. Analogous thermal signatures of stratified wakes were found in ocean observations and in modelling results. The influence of the tow ship on the wake was shown to be minimal. Laboratory experiments focused on the surface expression of stratified wakes were used to complement numerical simulations and field measurements. All three components of this project indicate that detection of the wake of a submerged object based on its thermal signatures is a viable and effective approach.Naval Research ProgramConsortium for Robotics and Unmanned Systems Education and Research (CRUSER)Office of Naval ResearchNPS-N16-N155-ANPS-FY17-N262-AN0001315WX0064

The remarkable effect of the 7-substituent in the diastereoselective oxidative rearrangement of indoles: Asymmetric synthesis of 3,3-disubstituted oxindoles

International audienceThe nature of the 7-substituent has a remarkable effect on the diastereoselectivity of the oxidative rearrangement of indole-2- carboxamides derived from (S)-2-methoxymethylpyrrolidine into chiral 3,3-disubstituted oxindoles