B.R.S.M. Tet. Lett. Is other people


A Funny Thing Happened on The Way To Hexaradialene

The last two weeks have seen me secure a postdoc in the US, pass my PhD viva and catch a nasty cold, leaving little time in my life for writing. Now that I've finally got a few spare hours I'm completely out of ideas for a post, so I'm just going to write about some nice oldschool mechanistic detective work from the 1970's that I came across recently. Enjoy!


Here's a tricky little problem that was set at the start of a postgraduate research symposium I attended back in July. It was printed on the programmes given out at the door with a deadline at the end of the two day conference and a cash prize up for grabs. So, all that was required for the glory and spoils was a mechanism that rationalised the following experimental outcome:

Once you've drawn a few things down, you'll quickly realise that the difficulty lies not in drawing a mechanism for formation of the product, but in getting those pesky labels in the right place.  Give it a go, and then read on for more information and the solution!

Filed under: Ask the audience, Literature | 13,865 views | 5 comments Continue reading

Four Days To Go!

From Chem. Soc. Rev., 2012, DOI: 10.1039/C2CS35116A

Just a quick post to remind you that I need your Colouring Competition entries by the end of Tuesday so I can write some kind of round up post in time for Nicolaou's birthday on Thursday. This weekend would be a good time to spend just 10 or 15 minutes messing around in Photoshop, the GIMP, or at a push, MSPaint. Heck, you can even print them out, colour them in and scan them if you don't have mad image editing skills. Not that it matters; I certainly don't. Give them to your children! If you're short of inspiration you can check out the entries from See Arr Oh and DrFreddy, or look at the latest Nicolaou review above.

Filed under: ANFSCD, Ask the audience | 11,085 views | no comments No Comments

A Birthday Surprise for K. C. Nicolaou

Update 1930, 20-06-12: Just noticed a mistake in my haplophytine structure (cdx, png and jpg) - a mesyl group where there should be an OH. If you've already downloaded/printed this please get the new, corrected version before continuing. Sorry!

Also, check out the first entry, from DrFreddy over at Synthetic Remarks!

Before you hurry to  check JACS, I made this myself. The image, that is.

The ongoing trend towards more colourful graphical abstracts is a perennial topic for discussion around the blogosphere.[1] Rather than draw attention to recent crimes against chemical decency, many of which can be found at TOCROFL, I am today proposing something new.[2] As many will know, the current spate of increasingly lurid abstracts can be traced to one man, American Cypriot and legendary synthetic chemist K. C. Nicolaou. But when did it all start? The cover of Classics in Total Synthesis I, published in 1996, appears to be free of such visual pollution, but it seems that by 2003 when Classics II and his autobiographical Tetrahedron prize essay were published that the inveterate colouring in had begun, and his papers are now rarely seen without it. However, I'm not going to join the online castigation of this questionable new form of art. Far from it. In fact, as it's KCN's birthday in a little over two weeks from today, I propose the WORLD'S FIRST CHEMICAL ABSTRACT COLOURING COMPETITION!

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Happy Birthday… To Me!

This is an actual cake that my girlfriend made me. I'd share it with you if I could!

Well, I didn't think that this day would come, but I have now been blogging for exactly one year! One rainy weekend last June, I sat down and wrote my first three posts, all on recent total syntheses. At the time, Totally Synthetic had been dormant for several months, and I planned to fill the void left by its absence. I only had about ten months funding left for my PhD, and I didn't know if I'd stay in chemistry after I finished, so I was entirely uncertain about where this site was going. In retrospect, it was probably a pretty stupid thing to start when I was supposed to be working my hardest in the lab to finish up.

Although I was pretty nervous at first, it turned out that very few people actually read my early posts, and I discovered that it's really hard to promote your own blog if you wish to remain anonymous. However, thanks to some advice offered in a comment by Freda I created a Twitter account, and after a few links and retweets by Nature Chemistry and New Reactions, I finally got some readers! Fast forward to the present and, as of this morning, this site has got been viewed almost 104000 times, which is a response I could never have imagined when I started. In my third post, See Arr Oh (in his homeless, pre-Just Like Cooking days) left me some very encouraging advice in a comment:

People are always looking (although they may not seem like it) for erudite but approachable discussions of the literature. Many just don’t have the time or access to look themselves, so they’re happy to have you guide them through it.

The niche takes a while (says the guy who doesn’t manage his own blog!). Just keep writing about good, current stuff, and people will find you.

How right he was! As I started to experiment with different types of posts, I was surprised to see that many people were more interested in shorter, more varied posts than the long, detailed total synthesis-based posts I'd planned to write. In fact, I'm not even sure how to describe this site to people any more - with posts from explosives to etymology, from chemical history and biographies through to the latest stuff you'll never try from slightly disreputable journals, I think I've shed my label of a poor man's Tot. Syn.!

Right, I'm not got to ramble on any longer, as people come here to read chemistry and I try to keep the personal stuff to a minimum. Many thanks to you all for reading, commenting and getting the word out! A special thank you to Dr Freddy from Synthetic Remarks, who offered me space on his webserver after my hosting became too unreliable, set me up with my own domain, and continues to host this site. I don't know what I'm doing next, but hopefully I'll be writing another post like this one next June!




P.s. More science soon! If anyone has any good tips for things worth writing about, or is interested in guest blogging here, please get in touch or leave a comment!

P.p.s. Should you wish to celebrate this auspicious day, but find yourself sadly incapable of making a cake, then here's the recipe that was used for the one above. It's just a regular Madeira cake that's been dressed up a bit, but was quite tasty. Although I love to cook, I don't make many cakes, so this recipe is courtesy of my better half. Enjoy!

Filed under: Ask the audience, Not Chemistry | 19,746 views | 9 comments Continue reading

A Funny Thing Happened On The Way To Hirsutene

Or: Why My Group Hate Me #13572

Apologies for the recent silence - I have just started a new (temporary) postdoc, and I have been busy with the reading for that. I am now an alkaloid chemist! The next few updates will be brief while I settle in.

Many research groups seem to have a weekly problem session, or something similar. In my experience, this usually means a rota (or something less formal) where people take it in turns to set a few chemical problems for everyone to have a go at. Often a sheet is produced, and handed out a few days before so people can have a chance to think/put the structures into Scifinder.

The problems themselves can vary a great deal, and are nowhere near as predictable as, say, undergraduate exams. A common layout is the 'synthesis blankout', where a synthesis from the literature is redrawn but some key reagents and intermediates are missing, to be filled in by the attendees. Alternatively, sometimes a bunch of short reaction sequences are taken from several papers, because they're interesting, or illustrate a particular theme. I've also seen a few more original approaches, such as this one, which I think I downloaded from the Ley group website a few years ago:

In the group where I did my PhD, the sessions were always run by students and postdocs, attendance was optional and the boss never came. Although you might expect that without a scary professor most of the group would go, as we all have to viva at some point, this turned out not to be case, and there was probably never more than a third of us present at any one time. I was a regular, and used to enjoy problem sessions - much like I enjoy crosswords, pub quizzes and, well, being an organic chemist - for the challenge. They're also a great chance to focus on chemistry outside of what your own group does. My PhD was on the synthesis of largely flat - and if not, racemic - heterocyclic natural products, so I tended to set questions about selective transformations in large, stereochemically dense molecules, in order to vicariously experience the thrills and tribulations of modern organic chemistry. Unusual or baffling transformations on seemingly simple systems were another favourite of mine, and I really enjoyed these recent offerings from DrFreddy over at Synthetic Remarks. In that vein, I offer you this question, which I recently set for my group:

Answers in the comments, or via Twitter!

Filed under: Ask the audience | 14,696 views | 9 comments 9 Comments

A Little Self Deprecation in Tetrahedron

This caught my eye while reading Tetrahedron this morning. At first I thought it was a mistake, but then I realised that it was also in the PDF as well, presumably okayed by the authors. I think it's pretty funny to see this title in the TOC with 'Orginal Research Article' next to it:

Strangely, the rest of the paper seems quite confident. I guess time will tell.

Filed under: Ask the audience, Current Literature, Fun | 31,301 views | 3 comments 3 Comments

Holiday Reading 1: Perspectives and Humble Beginnings

Thanks to DrFreddy and Young Padawan for providing the inspiration for this post! Happy New Year!

I have always enjoyed learning about the history of reactions and strategies; for me the who and when are often as interesting as the what as they put the chemistry in context, and often make things a bit easier to remember because they help with the big picture. Plus, we all like to have stories about famous chemists to tell when we get together over coffee (or beer).

Late last year an interesting discussion took place over at Synthetic Remarks, sparked by the autobiographical piece published by Stork in the Tetrahedron issue celebrating his 90th birthday.[1] The article itself is well worth a read for some interesting anecdotes interspersed with a little chemistry. I particulary enjoyed Stork's offhand description of his marriage:

"My progress in the lab was only moderately affected by getting married to Winifred Stewart, the same young woman that I had met at St. Petersburgh Junior College some years before. As I recall, I asked one of my lab partners to watch over a reaction while I went to meet my future wife in the office of the justice of the peace who was to marry us"

Well, I guess you don't get that good by wasting time on your personal life! I also liked the story of his and Woodward's recruitment as promoters for the journal Tetrahedron at its launch:

"...one event I remember was the launching of Tetrahedron. Captain Maxwell, as the editor of the journal in question was known, had invited in April 1957, a number of guests in a townhouse in downtown New York to mark that event. During the celebrations, Maxwell placed a bet with some of the guests, namely Bob Woodward, Bill Doering, Carl Djerassi, and myself that the circulation of Tetrahedron ‘will not exceed 2499 copies’ by April 24, 1961. The bet, which was witnessed by Sir Robert Robinson, was for 100 gold guineas. This was a clever bet, because Maxwell would essentially get four salesmen for his new journal in exchange for a relatively small amount of money. Time passed, and one day I received a phone call from Woodward who said ‘you know, we won the bet’. I did not know, but I eventually got a call from Maxwell who suggested I meet him in a townhouse downtown where, after some champagne, he gave me a copy of a letter from a bank in Basel stating that 100 gold sovereigns (the bet had been changed to sovereigns by mutual agreement) was waiting for me in the branch of the Swiss bank in New York. I went there, carrying a French newspaper that I thought would give me some appearance of respectability, and was introduced to a vice president who did, in fact, hand me a small bag containing 100 gold sovereigns. This, after many years, is worth quite a bit. In 2011, at the time of this writing, 100 gold sovereigns equal in excess of $30,000!"

There are also a number of the infamous 'car stories' for which Stork is quite well known.[2]

Following DrFreddy's post, commenter Young Padawan asked if anyone knew of  any other such pieces on the lives of famous chemists and a list was created:

Steve Ley:

Tetrahedron, 2010, 66, 6270-6292. (DOI: 10.1016/j.tet.2010.05.049)

Larry Overman:

Tetrahedron, 2009, 65, 6432-6446. (DOI: 10.1016/j.tet.2009.05.067)

Robert Grubbs:

Tetrahedron, 2004, 60, 7117-7140. (DOI: 10.1016/j.tet.2004.05.124)

K. C. Nicolaou:

Tetrahedron, 2003, 59, 6683-6738. (DOI: 10.1016/S0040-4020(03)00943-8)

David Evans:

Tetrahedron, 1999, 55, 8589-8608. (DOI: 10.1016/S0040-4020(99)00436-6)

Filed under: Ask the audience, Current Literature, Literature | 23,154 views | 10 comments Continue reading

Guess That Venue!

While sorting through the photos from last fortnight's conference/holiday I found this beautiful shot of the lecture theatre complex in which I gave my talk. It's not quite finished... but where is it? Answers on a postcard!

P.s. This is not a joke. I seriously attended a 4 day conference here. I like the yellow curtains on the right, leading up to the entrance. The phrase 'lipstick on a pig' springs to mind.

Filed under: Ask the audience, Fun | 28,693 views | 4 comments 4 Comments

Resources List

One thing I've been meaning to do for a while is put together a links page for online resources (other than journals or blogs) that might be of interest to postgraduate chemists. I've noticed a few times recently that I'll talk to someone about a particular reaction and then tell them there's a great explanation in Andy Myers' Chem 216 notes, Baran's heterocyclic chemistry handouts or Dave Evans' lectures and they'll just stare at me blankly. Likewise, a number of groups make their group meeting presentations freely available and I've learnt a lot from reading some of these. So, below are sites I've found to be useful, but I'm sure/hoping there are lots of good ones missing so don't be shy and point them out in the comments!

Filed under: Ask the audience, Serious | 25,191 views | 19 comments Continue reading

Projects I’m glad I didn’t work on

Obviously this style of post is borrowed from Derek Lowe's Things I Won't Work With. I'm not the most original person, and this certainly isn't the most original blog.

Hopefully many of you will have now read Baran's axinellamine paper (my take here) - it's an impressive piece of work and worth a few minutes of your time. I've noticed that I keep having the same conversation about it with different people over the last day or two:

BRSM: Have you seen Baran's new axinellamine paper? It's the shit!

Chemist: Yeah, it's pretty cool, but you couldn't pay me to work on that project. Those guys must have spent a lot of time staring off the roof of the Scripps chemistry building.

BRSM: But he's so sexy!

Chemist: I have to go now, I, uh, have a TLC running...

Or variations on that theme. Anyway, I realised that actually: 1. I'm probably inclined to agree, and 2. I find myself thinking this quite a lot. As I told commenter gippgig yesterday, I saw Baran give a talk about this work back in 2009. I remember him describing the silver(ii) picolinate oxidation and saying they had to screen a massive number of oxidants to find this successful reagent. I think he described one of his students as having a 'black tar phase' of 6 months or so, where everything presumably kept degrading when they attempted to install that troublesome hydroxyl. Silver(ii) picolinate obviously wasn't high on the list  of things to try as they had to make it specially, and none of the references they give for its use are later than the early 1970s. Periods of faliure come to everyone who practises chemistry long enough, but when you're pushing the boundaries of what's known, as Baran was here, you can spend months in the lab going nowhere at all.

A couple of other syntheses from this year with similar heroic efforts at optimisation come to mind. I should say now that I think they're both fantastic, but I'm not sure I would have had the dedication and mental fortitude to see them through.

Filed under: Ask the audience, Current Literature, Fun | 51,082 views | 19 comments Continue reading