Supergreen

This came out today in Org Lett from Shirakawa and Kobayashi. I think that the graphical abstract really explains everything:
Here there are two big things. First: this is actually a coupling of alcohols (including sugars) with neutral carbon nucleophiles (such as indole) that implies liberation of water (rather than halogen containing salts) as the only byproduct. But this is not a problem (here the second big thing), since the reaction is performed IN water (you've seen the Janda/Hayashi correspondence, didn't you?), at roughly 0.5M in both reactants. The catalyst is DBSA (dodecylbenzenesulfonic acid) and although the loading is still a bit high (yet typical for organocatalysts) and the reaction is performed at 80 C, to me this sounds like REAL green chemistry. Yields are good to excellent and if you get 94% you might not even want a chromatographic purification, extremely reducing the use of solvents. Nice, really well-done, we are already waiting for the enantioselective one...

Welcome to the new ONE!

I don't have much time now and I still have to check it carefully but I had a quick look to PLOS One which is finally online! The website looks amazing, I went through the 2 only chemistry articles (compared to 25 in genetics and 24 in infectious diseases), I cannot say much about the scientific level since I have no expertise in the fields but indeed at a first glance they look like proper papers! The annotations part looks well organized and the sandbox is definitely a good idea. The first funny thing I spotted is in the guidelines for discussion (point 7.3):

When previously published studies are cited, they must be accurately referenced and, where possible, a DOI and link to a publicly accessible version supplied.

Well, fine with the DOI but I'm afraid there are not too many publicly accessible versions of previous studies out there, hopefully it's just a matter of time.. I'll come back to this, in the meanwhile go and check it out yourself (I know you already did but I like to pretend being so ingenous..).

The catalyst factory

My main idea about this blog was to discuss some articles I particularly liked in the recent literature, I'll get started with two papers appeared in this week in JACS by Scott J. Miller and coworkers, one of the most active groups in the field of organocatalysis. The cool thing about the articles from this group is that they never emphasize too much the idea of "metal-free" catalysis. They rather focus on the development of really biomimetic transformations and they do it mainly using peptides (or amino acids). The first paper came out today and is about the employment of cysteine in the Rauhut-Curier (Rau-what? yes I reacted in the same way) reaction, which, roughly speaking, is an intramolecular Baylis-Hillman type of transformation.

I don't doubt that the products they get are synthetically useful but the interesting thing here is that they looked for an application of cysteine is catalysis starting from the idea that it is a very important nucleophile in biological processes. In fact, as far as I know this breaks the enamine-iminium paradigm for amino acid catalysts and it all seems very simple but nobody thought about it before (at least nobody reported that). The second paper looks more impressive at a first glance and deals with desymmetrization of a prochiral diphenylmethane having 2 OH groups separated by almost 1 nanometer.

Here they tackled the problem by first envisioning a catalyst based on a hexapeptide with aliphatic and aromatic sidechains to "match" the different regions of the substrate. They went on with some hardcore combinatorial synthesis and screening of many peptide candidates and finally they had a look at what are the unimportant parts of the catalyst. In the end they managed to obtain high ees with a relatively simple linear tetrapeptide.

Open Chemistry

I changed my mind and decided to write something about open access to publications in chemistry today. Open access is not a particularly popular idea among chemists yet, I'm afraid.. When PLOS launched PLOS Biology, their future plans included PLOS Chemistry. Unfortunately this long-awaited journal has been set aside as PLOS decided to focus on the life sciences. PLOS now publishes 6 highly respected journals: as an example, PLOS Biology ranked 1st for Impact Factor (14.672!) in the 2005 ISI Journal Citations Report. Their new journal Plos ONE, originally scheduled in late 2006, will publish contributions from all areas of science and medicine. The publishing model will be Open Access 2.0, consisting of a short peer-review aimed exclusively at a technical evaluation of the article. After that the paper will be immediately put online with the possibility to post comments and start a scientific discussion. The publication fee will be $1250 (now it is discounted at $750) and will not include editing (author's responsability). I believe it will take a while for PLOS One to become a highly respected journal for chemistry. Life scientists already know and trust the PLOS family. I think that in general chemists willing to publish freely accessible papers will prefer one of the options offered by the main publishers. As briefly mentioned in the previous post, the Royal Society of Chemistry launched Open Science in october and the first freely available articles should appear soon. After succesful peer-reviewing, authors can choose to pay a fee (£ 1000 for a communication from a non-member) and their article will be freely available to everybody. There is a very important detail distinguishing this (and the next examples) from the PLOS model: if the authors can not afford the publication fee, their article will not be available to non-subscribers. About the perspectives of open-access, RSC does not seem to share the PLOS enthousiasm and prefers a more cautious approach:

RSC considers the author-pays open access model to be an experiment rather than a proven business model. Running this model alongside the normal subscription route for access represents a risk, and the RSC reserves the right to withdraw the author-pays open access model at any stage.

The American Chemical Society did something very similar, allowing from october the authors to choose for open-access. Fees here range from $ 1000 to 3000, depending on the type of contribution and ACS Membership. On C&EN; News I found something about Elsevier giving an open-access option for 36 journals but I did not manage to find anything on their website. Actually, I found something dated 2004 going exactly in the opposite direction:

By introducing an author-pays model, Open Access risks undermining public trust in the integrity and quality of scientific publications that has been established over hundreds of years. The subscription model, in which the users pay (and institutions like libraries that serve them), ensures high quality, independent peer review and prevents commercial interests from influencing decisions to publish. This critical control measure would be removed in a system where the author-or indeed his/her sponsoring institution-pays. Because the number of articles published will drive revenues, Open Access publishers will continually be under pressure to increase output, potentially at the expense of quality.

In august Wiley started Funded Access (just to make clear that it becomes open upon payment) for some journals, mainly in the life sciences (yet including ChemBioChem and the Journal of Separation Science): standard fee is $3000. As far as I know, nothing like that is planned for Chem. Eur. J. or ACIE. Springer offers a similar option (Open Choice), also in this case the price is $3000. Finally, Thieme fiercely rejects Open Access, as clearly shown in this reply to an EC study on scientific publication markets, which had as first recommendation to "guarantee public access to publicly funded research results shortly after publication."

Chemistry journals on the web

I succesfully managed to import my Google Shared Items with what I like in the Advance Articles for a number of journals. Of course, to make this possible, RSS Feeds are required and although most publishers offer feeds for their journals there are some important exceptions. I'll start from the bad ones: Thieme and ScienceDirect. The Synlett/Synthesis website is possibly the worst for organic chemistry. I did not expect to find RSS and indeed I was right. After all, they do not even have a search option in the website! The Tetrahedron family goes a bit better but not too much. If you google "ScienceDirect RSS" you get this. There are only two Live bookmarks, a newsletter and the unbelievable "Title Alerts", a feed informing you on "New, Changed and Discontinued Titles" (makes sense? really? only for libraries, I'm afraid). I considered subscribing to that, maybe in a while they will discontinue the Tetrahedron family, it will be good to know. I personally hated the Tetrahedron pages long before the recent redesign, especially the fact that back issues were sorted by volume number and not by year (which is what I use to find references). I think providing the user with a feed about Advance Articles is important to increase the interest in a journal and Elsevier should do something about that as soon as possible. Wiley Interscience goes much better, although my feeling is that they're doing as much as they can to make it fancy rather than practical. Look at this, did you really need to know that many users are looking for "homogeneous catalysis"? They'd better figure out an easy way to retrieve the citations for the german version of Angewandte Chemie once you know the page numbers of an article on the International Edition, possibly something better than this:

Q: I have a reference for the German edition of Angewandte, how do I find the article in the International Edition (and vice versa)?

A1: In Wiley InterScience, locate the article in the German edition and click on "Find articles in Wiley InterScience written by any of the authors" at the bottom of the abstract page. Of course, this also works the other way.

A2: Use the CrossRef search form, enter only "Angewandte" as a title, the first author's name and the year of publication.

Moreover, they could make the graphical abstracts freely accessible, like everyone else does.. One more thing about their graphical abstract in PDF, they could put links to the articles in the PDF, should not be too difficult, right? The Royal Society of Chemistry has a good website, pretty straightforward and with proper search functions. The only thing is that it opens too many windows when you access an article or the graphical abstract. And I don't understand why they do not make PDFs available for the Advance Articles, I personally hate to read scientific literature in HTML. The RSS Feeds are the best in chemistry, together with the ones from ACS, giving you a graphical abstract, ideal for a quick check of the literature while you're drinking your 10th cup of coffee. By the way, RSC is launching something very cool, exploiting the little interest of PLOS for chemistry, stay tuned as this will be the topic for one of the next posts (maybe after PLOS One takes off and we see what it lookes like). The American Chemical Society has an excellent website, everything is easy and I think they should exted the redesign of the JACS page to all the other journals As Soon As Possible (did they really need to register the service mark?). One hilarious thing about the websites of JACS and ACIE is that both happily claim to be the the best chemistry journal in the world. JACS has the highest number of citations while ACIE the highest impact factor. To prove that this is not the result of having reviews, minireviews, highlights and essays, people at Wiley engaged in a pretty extravagant demonstration you can find here.

Let's get started...

Hi everybody and welcome to levorotation. If you got here believing to find something exciting I'm afraid I'll have to disappoint most of you as this is a chemistry blog. As the title suggests, most of the stuff will be about asymmetry, which personally I consider the most exciting topic in (organic) chemistry. I thought about putting here one of those horrible pictures with the two hands and the mirrorplane in between (or the two oppositely handed shells) but that would be too cheap for a blog on chirality so I'll rather work on the settings..