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Raging Hormones – Gram-Scale Synthesis of Prostaglandin PGF2α

“Stereocontrolled organocatalytic synthesis of prostaglandin PGF in seven steps” Coulthard, G.; Erb, W.; Aggarwal, V. K. Nature 2012, online view. DOI: 10.1038/nature11411

In my very un-scientific survey of the green chemistry-branded journals, I see way more new methodologies than I see total syntheses. I hope to single-handedly change this, and show how green a total synthesis can be by writing about the awesome recent synthesis of prostaglandin PGF by Aggarwal and coworkers. First, a few words on the target molecule. Being hormones, prostaglandins such as PGF are involved in tons of biological processes. Interestingly, instead of being synthesized by some important gland and acting in far-off regions of the body as are endocrine hormones, they are autocrine or paracrine hormones and are synthesized “on-site.” The first structural characterizations of prostaglandins came in the 1960s, some 30 years after their initial discovery. Soon after, they became the subject of numerous syntheses, the first of which was achieved by E. J. Corey in 1969. A series of syntheses followed, but even 40 years later, the structurally-related glaucoma drug latanoprost is synthesized in 20 steps using Corey’s 1969 prostaglandin strategy.

That’s right, the prostglandin structural motif is medicinally relevant. So, not only would an improved synthesis be cool from a fundamental science perspective, it might actually be moved into industrial production and have an immediate impact! Continue reading

Materials, Synthesis

A “Designer” Surfactant for Cross Couplings of Hydrophobic Reagents in Room Temperature Water

“TPGS-750-M: A Second-Generation Amphiphile for Metal-Catalyzed Cross-Couplings in Water at Room Temperature” Lipshutz, B. H.; Ghorai, S.; Abela, A. R.; Moser, R.; Nishikata, T.; Duplais, C.; Krasovskiy, A.; Gaston, R. D.; Gadwood, R. J. Org. Chem. 201176, 4379-4391. DOI: 10.1021/jo101974u

I occasionally run reactions in water, and it is awesome. I LOVE not worrying as much about cancer. Unfortunately many interesting chemicals are simply too hydrophobic to allow reactions to be run in aqueous solution. As anyone who has ever scrubbed a greasy pan will know, one way to get around the solubility problem is with soap. Also called emulsifiers, surfactants, amphiphiles, a soap by any name is pretty much the same thing in my mind (though others will disagree I’m sure). Molecules with hydrophilic and hydrophobic ends can form micelles in water, creating variously-shaped and sized particles with hydrophobic cores. Using those hydrophobic cores as reaction media is a concept known as micellar catalysis. The Lipshutz group was not the first player in this arena, but they have been at it for some time. They recently teamed up with the medicinal chemistry company Kalexsyn and came out with a new amphiphile that caught my eye, dubbed TPGS-750-M. 

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Toxicity Prediction via Hard-Soft Acid-Base Theory

“Application of the Hard and Soft, Acids and Bases (HSAB) Theory to Toxicant–Target Interactions” LoPachin, R. M.; Gavin, T; DeCaprio, A.; Barber, D. S. Chem. Res. Toxicol. 201225, 239-251. DOI: 10.1021/tx2003257

I considered posting about the Carreira group‘s work on enantioselective amination of allylic alcohols, because I think it is an awesome example of direct functionalization of hydroxylated substrates–an issue that will be of increasing importance in terms of biomass utilization. However I chose instead to stray into the less familiar territory of the bioactivity of organic molecules. I am semi-familiar with quantitative structure activity relationship (QSAR) modeling, wherein a database of known molecules and their bioactivity is used to predict the bioactivity of a molecule about which there is no bioactivity data. However, relying solely on computers leaves me wanting a more intuitive grasp on which molecules are expected to be toxic/non-toxic and why. That’s why I got excited about the recent perspective article about using the familiar Hard-Soft Acid-Base theory to predict toxicant-target interactions.

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Materials, Synthesis

Inherently Flame-Retarding Polymers

“Preparation of flame-retarding poly(propylene carbonate)” Cyriac, A.; Lee, S. H; Varghese, J. K.; Park, J. H.; Jeon, J. Y.; Kim, S. J.; Lee, B. Y. Green Chem. 2011, 13, 3469-3475. DOI: 10.1039/C1GC15722A

During graduate school in California I was very aware of the tremendous amount of household furniture loaded with flame retardant polybrominated diphenyl ether chemicals. Those chemicals do a great job of reducing the flammability of numerous petroleum-based products. Unfortunately their non-covalent incorporation in the polymers speeds their environmental release.  Once in the environment, they break down slowly and bioaccumulate. Additionally there are numerous human health and ecological concerns with these chemicals, including their association with decreased fertility in humans (ref). That is why this paper on flame-retarding poly(propylene carbonate) (PPC) caught my eye. Another reason could have been the flames in their graphical abstract!

TDI = toluene 2,4-diisocyanate; TPU = thermoplastic polyurethane

As luck would have it the chemistry is neat too, flames aside. The researchers begin by highlighting (bragging about?) the fact that they have an actual pilot plant in which they use their cobalt-salen-based catalyst to polymerize CO2 and propylene oxide to PPC (Note: experiments from this study were not performed in the pilot plant). The catalyst displays high turnover frequency (15,000/h) and produces high molecular weight polymers (Mn = 300,000).

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Environmental Chemistry, Materials

How Robots Can Help Us Understand the Environmental Fate of Nanoparticles

“Assessment of the physico-chemical behavior of titanium dioxide nanoparticles in aquatic environments using multi-dimensional parameter testing” von der Kammer, F.; Ottofuelling, S.; Hofmann, T. Environ. Pollut. 2010, 158, 3472-3481. DOI: 10.1016/j.envpol.2010.05.007

In order to rationally design nanoparticles that are environmentally benign, we need to be able to accurately predict their environmental fate (i.e. will they travel long distances through waterways, get stuck in soils or sediments, etc?).  Though relatively robust modeling tools are available for predicting the environmental fate of organic chemicals, analogous tools for nanoparticles are in their infancy.  This is largely due to the insane variety of nanoparticle properties (e.g., composition, size, shape, surface chemistry, etc) that can be varied, resulting in an equally insane variety of nanoparticles to study.  In addition, we know very little about any of these nanoparticles.  One important property that controls the environmental fate of nanoparticles is their propensity to aggregate together and fall out of suspension, potentially limiting their environmental mobility.

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Catalytic Directing Groups in Hydroformylation

“Synthesis of Quaternary Carbon Centers via Hydroformylation”  Sun, X.; Frimpong, K.; Tan, K. L. J. Am. Chem. Soc. 2010, 132, 11841.  DOI: 10.1021/ja1036226

Just as the advent of protecting groups opened up new chemical space accessible by current synthetic techniques, so too did the advent of the directing group.  Both however come with the downside of often requiring additional synthetic steps for the installation and removal of these groups.  For example, the past decade or so has seen a number of efforts at using directing groups such as phosphines to affect the course of hydroformylation reactions.  I should mention here that people are so interested in the hydroformylation of alkenes in part because it is such an industrially important reaction, with 9 million tons of aldehyde products being produced in this way per year (ref).  The challenges with this reaction are selectivity, one of the foremost issues being that terminal alkenes preferentially give linear products.  Shown below is a 2001 example from the Leighton group where a phosphine directing group on allylic ethers yields the branched hydroformylation product (Markovnikov addition), whereas the linear product (anti-Markovnikov) would be favored in the absence of the directing group:

The Up-Side: this method offers access to substrates not previously available through hydroformylation.   The Down-Side: it is hard to imagine an industrially-relevant product containing that specific phosphine moiety, so it would undoubtedly have to be cleaved, making the overall process highly atom un-economical.  This latter point could be addressed by somehow using the phosphine group in a catalytic, instead of stoichiometric, fashion.  This is exactly what the research group of Kian Tan at Boston College has been up to lately.  They have developed what they term a “scaffolding ligand” that coordinates to the organometallic catalyst as well as rapidly and reversibly (two important things for this type of catalysis) forms covalent bonds with alcohols.  In doing so it brings the substrate (in blue below) and catalyst (in red below) in close proximity and influences the course of the reaction.

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