1. Report honest results and record those results, and the procedures required to obtain those results, in their lab notebooks.

2. Behave professionally, both in demeanor while working in the lab and in their interactions with colleagues. This includes maintaining the correct work ethic, hours, and keeping racism, sexism, or any other interfering 'isms' out of the mix.

3. Behave morally and ethically, and at a minimum, not interfere with the work of others.  Contributing to a supportive learning and work environment is preferable.  This is intricately tied to #1, and the 'isms' in #2 matter here also.

4. Uphold any group duties they are responsible for performing to help keep the lab running smoothly.

The case is a huge lesson in #1 and #3 - honesty and morality don't necessarily go hand-in-hand with science research, and unfortunately, it's a widespread problem (in anything involving humans!) that is only exemplified by what happened at Columbia.  In the instance of #1 - Yields are being inflated EVERYWHERE.  Yield and %ee inflation are a huge problem in the field of organic chemistry overall.  I know of labs where several natural products chemists have been known to add small amounts of NMR traceless material to intermediates that won't be submitted for elemental analysis or x-ray to inflate their yield.  (Why bother if you can just fudge the number on the manuscript?  Some prefer to just go that route.)  Small 1H NMR peaks are unassigned and thus reported as impurities, where they are actually part of the structure.  If reactions are performed multiple times, the best yield is reported. This goes for methodology reactions also, where the PI requires that the reaction be repeated several times.  PI's often don't respect or favor students who do not produce phenomenal results, and high-pressure, pre-tenure, or frequently-publishing labs aren't the place you want to be if you can't get your reactions working.

Don't even get me started on #2.  An example of the breakdown of #2 (professionalism) and #3 (morality & ethics) is a recentracism issue - it's clearly not dead, either, especially in a field where up to half of group members or post docs or research scientists aren't American, and I bet every one of you reading this has an anecdote for that, be you American of any race, or not.

This crap makes me want to scream.

For #3... there are labs where people lock their notebooks in their desk drawers to protect their ideas and their chemistry from their own group members.  People lock group glassware in their drawers to prevent access as well.  Maybe that's annoying, but members of labs actually go out of their way to feed misinformation, or omit crucial information, to other group members who need to reproduce the work (in examples where the chemistry DOES work). I know of one example recently where a new post doc joined a group and couldn't get a particular reaction to work with the conditions he was given, and only AFTER being given some crap by his PI did the people who gave him those conditions pretend to say "oops, we forgot to tell you about this crucial ingredient that is required for this reaction to work."   Surely you know of a story where someone has spiked someone's air-sensitive reaction with D2O?  I know I'm not the only one who is collecting these types of accounts just by being in an organic lab and in graduate school.

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Of course a PI is accountable for anything happening within the realm of their lab, but in truth, it is literally impossible to micromanage or keep track of every solitary day-to-day activity and movement of every person in their group, regardless of the size, but especially if it is a 15+ member group.   Let's just admit it - not all PI's go over every piece of data, every spectrum, and every word in a Supporting Information file, because, perhaps, they've seen the project progress, know where the pitfalls were and how the student(s) dealt with it, and thus trusts the student(s) to report accurately.  I know of many faculty members who don't read Supporting Info of papers they submit, either because they trust the students, don't have the time to read them, or are so famous and busy that it doesn't even occur to them that they should be doing that, if they even care.  (How many times have you tried to reproduce a simple prep and found yourself unable to get anywhere near the reported yield? There's a good chance that it was inaccurately reported because of crap like this.)  We can use the Sezen example to say Sames was a shitty PI for not looking at the data, but in that case, it's possible that looking at the data wouldn't have revealed jack because of how thorough her deceit was, especially if the spectra with the white-out didn't happen to be those under review!  He has since changed his ways (see in comments to the blogs linked above), but others haven't necessarily learned from his example.

What about what students rely on their PI to do?  This is arguably more complex, because there are probably more variants of PI-styles than there are student-styles.  In my opinion, PI's are expected to:

1. Monitor their students and post docs. At a bare minimum, know what project they are working on, at what stage of the project they are in, and be aware of any problems occurring.

2. Monitor their laboratory.  Designate individuals to be in charge of duties, keep updated on the function of instruments and equipment, and otherwise be aware of whatever necessary to keep the lab running smoothly. Enforce group rules and performance standards.

3. Same as for students:  Behave professionally, both in demeanor while working in the lab and in their interactions with colleagues. This includes maintaining the correct work ethic, hours, and keeping racism, sexism, or any other interfering 'isms' out of the mix.

4. Same as for students: Behave morally and ethically.  Contributing to a supportive learning and work environment is preferable.  I wish I could add 'treat lab members like human beings' but that might be asking too much.

5.  Publish in a timely fashion, and make sure that students are on a path that will result in some sort of publication.

6. Acquire $ to run lab.

7. Communicate with group members the expectations the PI has for them, and communicate if/when those expectations aren't being met.

We trust when we select a PI that they will meet these bare minimum requirements, using word-of-mouth as a primary tool the majority of the time to learn about a certain professor's reputation as a PI.  Sometimes that's not enough, and people find themselves switching groups when they aren't happy with their lab or PI - it happens, and hopefully departments are amenable to that kind of necessary switch in the event of a student-PI mismatch.  Selecting a PI has grave consequences on the next 5-6+ years of our lives directly, and indirectly on the rest of our careers.   It's not just about the science, it's about our futures, the rest of our so-short, singular lives.  Arguably, a PI has more influence on his or her students' lives and careers than vice-versa, so the obligations of the PI in control/power/position of authority are paramount to uphold.

Sadly, despite the obligation a PI has to see his/her students through their career in graduate school, we still see students getting kicked out of labs at the start of their 5th year for no explicitly stated reason, not allowed to return after a medical or personal leave of absence despite not disclosing that possibility, women and men being treated unequally (either better or worse depending on the PI), not at all supervising their students or maintaining a presence in the lab, letting research papers ready for publication sit on their desk for multiple years until it's too late to publish it, etc.  I'm in my fifth of six years in my program, and I can't even begin to describe the absolute bullsh#* I've witnessed in the treatment of graduate students.  I used to think that senior graduate students were jaded because of how hard they worked for so long - but for me, it's not so - it's because of what I've seen go on around me and experienced first-hand moreso than how intellectually and physically exhausted I am.  The bottom line is that there is no accountability required for PI's the way there is for students, and tenure has everything to do with it.  It forces labs to churn out results and be amazing, which puts pressures on everyone involved, and then if and when tenure is obtained, inadequate performance won't necessarily lead to consequences (other than the obvious detriment to the career of whoever is involved).

 

But what can we do, besides trust that our PIs will help us get to where we need to go?  Trust that more often than not, PI's are functional human beings who treat everyone else like human beings and care enough about the people and the science in the lab to pay attention?  Usually, this is the case, but there will always be people, projects, and situations that fall through the cracks.

I doubt graduate students or post docs are buying many of these.

Trust is an issue in science because science is performed by human beings.  Trust is an issue because money, careers, and reputations are at stake, and there is no way that the PI's that run labs can be privy to every event that occurs under their watch without sacrificing other duties (particularly #5 and #6, getting $$ and publishing, and teaching also).  Science requires that knowledge either be discovered or that it be created, and it requires that it happens swiftly and elegantly.  In order for us to keep up we have to trust that our PI's will do right by us in the ways I've mentioned and they have to trust that we will do right by them in the ways I've mentioned, and everyone hopes the dynamics are functional and continue to be so.  Money seems to be the root of all evil here - pushing us to achieve, publish, succeed much faster than we can even acquire results, so that we can fund the continuing cycle.  Honest, hardworking faculty often don't get tenure because they aren't ruthless enough, don’t make strategic “friends” and develop collaborations, don’t play politics correctly in their department or field, don't publish enough or aren't creative enough - and therefore don't get the funding they need to succeed.  (How much of it is luck, anyway?)  As long as limited funding makes us as motivated as we are to publish our science, and as long as we all are human beings, we are going to have to trust each other to do and publish good science.  There's only so much policing that can be done here.

The chemistry that Fagnou has truly spearheaded, direct C-H functionalization, is a method of forming C-C, C-N, C-B, etc bonds without having to prepare one of the coupling partners, as in traditional transition-metal catalyzed cross-coupling reactions. Palladium, rhodium and ruthenium are commonly used catalysts in direct C-H functionalization reactions. Fagnou has published a great deal on arylation reactions of a wide variety of substrates and even a bit on direct benzylation reactions. Some fairly recent reviews are linked in a previous post at my own blog.

A recent publication in Journal of Organic Chemistry (doi: 10.1021/jo102081a), "Predictable and Site-Selective Functionalization of Poly(hetero)arene Compounds by Palladium Catalysis," published by David Lapointe and coworkers, explores the development of two approaches to selectively functionalizing multi-ring systems - 1) using site-selective reaction conditions, and 2) a pathway with a particular order of reactivity according to a concerted metalation-deprotonation (CMD) mechanism. It is well-known in the field that a great many (hetero)arenes can be functionalized with (painfully) rigorous fine-tuning of the catalyst, ligand, additives, and other reaction conditions. Some substrates have been more difficult to functionalize than others, and selectivity of particular positions on these rings is always an issue - this publication tackles both issues.

To explore site-selective functionalization, the group used compounds with more than one available C-H bond for direct functionalization, and using multiple protocols specific for specific C-H bonds (Larossa's conditions for C2 arylation of indoles, Gaunt's Cu-catalyzed C3 arylation of indoles which is actually selective for meta to amido groups, and their own protocols for arylation of perfluorobenzenes and aromatic N-oxides) were able to successfully and selectively functionalize targeted C-H bonds in moderate yields. Here is an example with some decent yields, with reaction times ranging from 16 - 24 hours:

The alternative approach relies upon the CMD pathway as the operative mechanism, which favors electron-deficient substrates.  Several years ago, Echavarren published support of this mechanism by finding a preference for the most acidic C-H bond and requirement for a carbonate base, and Fagnou established the use of a pivalate additive, which was speculated to play a crucial role via CMD.   A recent mechanistic paper with aromatic N-oxides as the substrates strongly supports this mechanism.   The metal first inserts into the aryl-X bond, as expected, and in the key transition state, the pivalate coordinated to the metal deprotonates the C-H bond while the palladium forms a bond to the same C.  Reductive elimination (not shown) releases the arylated product.

In the current paper DFT calculations were found to agree quite well compared to competition reaction results of a series of heterocycles to elucidate the order of reactivity of the substrates.  Those presented in the paper are as follows, in order of reactivity - this is extremely convenient for the synthetic chemist who would like to utilize this chemistry.  And it's just plain neat - the kind of thing that will hopefully end up in a textbook someday. (Note: the last two substrates are either switched in the text or switched in the image - they don't agree in the paper and I haven't looked at the supporting information closely.)