About

All Things Metathesis was developed by Materia, Inc. for the two-fold purpose of establishing a knowledge resource on olefin metathesis and providing a setting for the growing number of metathesis users to discuss the technology. In light of the company’s evolving expertise in the area of olefin metathesis, Materia is committed to educating the academic and corporate communities on the benefits and applications of this Nobel Prize winning technology. All Things Metathesis provides general information on olefin metathesis and specific information on ruthenium based metathesis catalysts.

Contributing Authors

Andy Nickel

Andy Nickel
Andy grew up in the suburbs of Philadelphia and attended Temple University as an undergraduate. In college he studied chemistry and spent his free time playing rhythm guitar in a band. One day, he skipped band practice to attend a graduate student literature seminar entitled, “Ruthenium-Catalyzed Olefin Metathesis.” Despite the teasing he received from his band mates that day, he still spends much of his time thinking about this very topic. After earning his Ph.D in 2005 from Yale University in the field of natural product synthesis, Andy worked as a medicinal chemist for 3 years before joining Materia in the summer of 2008.

jb_bourg

Jean Baptiste Bourg
Jean-Baptiste (J-B) was born in Ambilly, France and grew up in the French Alps, where he especially enjoyed skiing. He studied chemistry in Paris, earning an engineering degree from Chimie ParisTech, and did research on ruthenium-catalyzed hydrogenation. The weather in Paris being a little too rainy, he decided to move to Riverside, California. He spent the next four years trying to isolate diradicals and carbenes, and eventually completed his Ph.D. Willing to apply his knowledge on carbene chemistry to olefin metathesis, J-B worked with Prof. Grubbs before joining Materia in fall 2008.

paul_boothe

Paul Boothe
Paul grew up outside Pittsburgh, PA and began his chemistry career as a lab assistant for a cranky graduate student at Carnegie Mellon University, before becoming a slightly less cranky graduate student himself while obtaining his Ph.D. at the University of Southern California. After a brief stint in the classroom, he retreated to the safety of the laboratory, joining Materia in 2006.

diana_stoianova

Diana Stoianova
Diana grew up in Sofia, Bulgaria and got her Masters degree at Sofia University. After she earned her Ph.D. in organic chemistry from the University of Zurich in Switzerland she moved to the States for a post doc and never left. She ran her first metathesis reaction in Paul Hanson’s group at the University of Kansas, the reaction worked really well and everybody else in the group started doing metathesis. Diana joined Materia in the fall of 2002.

Daryl Allen

Daryl Allen
Daryl was born and raised on the east coast of Canada, in the small town of Woodstock, New Brunswick. Next was the move to the big city of Fredericton, to attend the University of New Brunswick and study chemistry. Besides chemistry, Daryl occupied his time by playing numerous sports such as baseball and hockey. To pay the bills, he worked at a local ice rink as a Zamboni driver, which is one of his main claims to fame in his native country!! After completing his Ph.D. in organometallic chemistry split between the University of New Brunswick and Queen’s University in Kingston, Ontario, Daryl moved to Pasadena, CA to work as a post doc with Prof. Grubbs and then joined Materia in the spring of 2008.

Rosemary Conrad Kiser
Rose was born and raised in Philadelphia, PA where she discovered her interest in chemistry from cooking and developing black-and-white photos. She then picked up and moved west to attend UC Berkeley for college and it was there that she ran her first metathesis reaction (ring-closing). After completing her PhD at Stanford in early 2008 in natural product synthesis, she moved to Southern California and joined Prof. Grubbs’ group for postdoctoral research. There she focused on ring-opening metathesis polymerizations (ROMP) and subsequently joined the team at Materia in early 2011.

Brian Conley
Brian grew up just outside of Charleston, W.V in a small town called Dunbar. Through high school, his main goal was to become a professional soccer player. It’s a good thing he also focused on his school work! Brian gave up soccer and studied chemistry at Elon University, getting involved in undergraduate research in the process. With new goals in mind, he made his way to the University of Southern California and obtained his Ph.D. in organometallics in 2008. Life in SoCal was too good, so he continued his training by doing a post-doctoral fellowship at USC before joining Materia in August 2011.

John Phillips
John grew up in the coastal city of Oceanside, CA and spent most of his time at the beach. He attended UC Berkeley for college and then landed in the “Berkeley of the Midwest”, where he completed his Ph.D. at the University of Wisconsin. In 2006 he once again returned to southern California to do postdoctoral research in the area of natural product synthesis at CalTech. After another stint in the Midwest at the University of Michigan where he lectured undergraduate organic chemistry and studied nickel catalysis, he moved back to southern California and joined Materia in 2010.

Nick Rodak

Nick Rodak
Nick was born and raised on the East Coast in the snowy confines of Attica, a small hamlet in Western New York. After too many episodes of “All Creatures Great and Small” growing up, he applied to and was accepted into Cornell’s veterinarian program. However, trudging through the howling winds of Ithaca brought back memories of many a cold, January blast while growing up on the farm that made him realize perception was attempting to define his reality and future. His first college Chemistry lab was an eye opener as he found he was not only memorizing, but was asking, experimenting, and learning. He never looked back, switched his major to Chemistry, and did undergraduate research for nearly 3 years, even foregoing a semester of study in France to catch up on graduation requirements because he didn’t want to stay longer…Only to end up staying longer for his Ph.D. at Cornell in organic and polymer synthesis, often joking he was “never told to leave so he kept showing up…” His first professional job took him to Valley Forge and, needless to say, even more snow. He finally escaped the East Coast and moved his family to the West Coast and the sun to join Materia in the spring of 2010.

About Materia, Inc.

Materia, Inc. was founded in 1998 to commercialize olefin metathesis catalyst technology. To that end, the Company has developed an extensive intellectual property portfolio, which includes over 350 issued and pending patents (worldwide) covering not only ruthenium catalyst composition and manufacture, but also methods of using the technology to perform a wide variety of transformations and compositions of certain products.

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{ 17 comments… read them below or add one }

1 Cezary Samojlowicz November 20, 2009 at 5:44 am

I would like to suggest a new topic about Fluorinated Aromatic Hydrocarbons.
In 2007 we found that reaction performed in such fluorinated solvents (eg. hexafluorobenzene) improved difficult metathesis reactions.
http://www.rsc.org/publishing/journals/CC/article.asp?doi=B816567J
Currently we are working on explanation this phenomena. It is not that easy.
I would appreciate put a new topic about Fluorinated solvents on your website.
People who working in olefin metathesis (and not only) could give some nice hints and comments about this unprecedented phenomena.

Best regards
Cezary

2 nickel November 24, 2009 at 1:12 pm

This is definitely an interesting phenomenon, Cezary, and is a good idea for a posting. A few examples have popped up the past couple of years where perfluorinated solvents show advantages, and to my knowledge no one has yet explained why. I’m glad to hear that the Grela group is working hard on this question!

3 Chris Thomas February 3, 2010 at 9:53 am

Hey guys, I just saw this reaction come out in Organic Letters today. It’s a Lawrence Williams paper, where it looks like he’s metathesizing two Type-I olefins? The interesting thing is they run the reaction over 7 days, using altogether 5 mol% while adding in 5 mg portions (41 mg total) every 24 hours. I’ve never seen such a gradual addition before and wouldn’t the catalyst die much faster than just 24 hours? Or having the small amount keep the catalyst turnover from decreasing, thus allowing metathesis to occur over the whole 24 hours?

Chris

4 nickel February 6, 2010 at 12:13 pm

One of the substrates is better classified as a Type II olefin due to the secondary allylic OTBS group, so the good selectivity isn’t too surprising. But the rate of catalyst addition is curious indeed. It’s also interesting that “bulk” DCM is a better solvent than DCM that was purified with an alumina purification system. Any thoughts as to why?

5 Chris D February 12, 2010 at 8:53 am

Hi folks,

Great job on this blog. Your posts are nicely written and cut to the chase to present some important observations.

One item of interest to me: Are you aware of any studies/reports on the effects of Ru (e.g. metathesis catalysts or their byproducts) in various bioassays– either in-vitro or cell-based screens? It’s not something I worry about too much, but it would be nice to have some definitive answers for people, particularly with regards to cellular toxicity.

Thanks!

6 nickel February 17, 2010 at 1:57 pm

Chris,
I haven’t come across a report of if/how metathesis catalysts interfere with bioassays. If you find one, let me know!

7 milkshake February 18, 2011 at 7:40 am

Andy, please can you drop me an e-mail, I have a chemistry job-related question.
Best, Tomas

8 Matt June 19, 2011 at 11:13 am

Hi guys,

Nothing much to add in the way of interesting questions that you might be able to investigate, but I just wanted to let you know I’ve found this website a really good and strong resource of information for my work into RCM; not just as a collection of literature, but also as a source of practical information. Also, in general I find the articles all to be enthusiastically written – metathesis certainly is an exciting area to be involved in!

Regards,

Matt

9 nickel June 20, 2011 at 12:47 pm

Much thanks, Matt!

10 Matt December 9, 2011 at 8:18 am

Hello again to everyone at ATM.

I put my RCM work to one side for a few months, but now I’m back on the attack to work on increasing yield through optimisation of work-up and isolation. One idea that occurred from my discussion is solid-supported ruthenium catalysts for RCM; has such an idea been entertained and investigated? I would assume it has been, but I can’t seem to find anything in the literature (apart from examples where the substrate to be ring-closed is tethered to a solid support!)

I’m open to email discussion on this!

Matt

p.s. merry christmas

11 Daryl December 16, 2011 at 11:31 am

Matt,

Here are a few review articles to check out regarding solid-supported olefin metathesis catalysts:

(1) Coperet, C.; Basset, J.-M. AdV. Synth. Catal. 2007, 349, 78–92.
(2) Clavier, H.; Grela, K.; Kirschning, A.; Mauduit, M.; Nolan, S. P. Angew. Chem., Int. Ed. 2007, 46, 6786–6801.
(3) Buchmeiser, M. R. Chem. Rev. 2009, 109, 303-321.

Also, another great resource is the review article by Grubbs and Vougioukalakis:

Chem. Rev. 2010, 110, 1746-1787. This is just a great review article in general, but specifically section 10 details some supported catalyst work.

Also, feel free to check out a paper that a co-worker and I published with Grubbs a few years back:

Org. Lett. 2009, 11, 1261-1264.

Perhaps here at ATM, we should do a posting on some solid-supported catalyst work…look for that in 2012.

Thanks for the interest Matt! Best of luck with your project!

Daryl

12 Matt December 16, 2011 at 12:21 pm

Thanks very much Daryl – I’ll be sure to read those papers!

Matt

13 Jake March 13, 2012 at 11:36 am

Very interesting to see Materia’s growth. Curious to know what the future of the company is?

14 Scott August 17, 2012 at 4:05 pm

Hi Guys, i’m using metathesis for the first time and I was pointed in the direction of this site, seems to be a fantastic resource from my reading so far.

Unfortunately so far the reaction i’m attempting is not working. I am attempting form a stillbene via an RCM macrocyclisation of two terminal styrenes, the macrocycle is an 19 membered ring which contains a couple of peptide bonds.

So far I have refluxed the reaction in DCM at 0.002M concentration (after degassing thoroughly) with 5% Hoveyda-Grubbs 2nd gen. By TLC and mas spec I can only see starting material, so I guess initiation is an issue!? For my next attempt i’m going to try toluene (for increased temperature) and increase the concentration (perhaps the concentration of catalyst is just too low).

Any thoughts or if you can think of any publications which may be of use I’d really appreciate it.

Many thanks

Scott (a desperate 4th year PhD student)

15 Daryl Allen August 27, 2012 at 4:13 pm

Scott,

This is definitely a challenging reaction that you are describing. I think your choice of catalyst is correct going with the 2nd gen Hoveyda-Grubbs and I like your idea of using toluene and increasing the temperature of your reaction. Have you tried this yet? How did this work?

In terms of a few other suggestions to try:

(1) I’m not sure if the amines in your substrate are protected or not but I would suggest trying that if you haven’t.

(2) It may be worthwhile to investigate sparging your reaction mixture with an inert gas to aid in the removal of any generated ethylene. Likewise, you could try running the reaction under static vacuum to do the same thing.

(3) if things still aren’t working at this point, you can always increase your catalyst loading and see if you get any productive RCM

Keep us posted here and best of luck!!

Daryl

16 Mohammad Asgar Khan May 22, 2014 at 10:29 am

Hi

I found this blog and writings very interesting. I am trying to do ROMP reaction with 5E2N (5-ethylidene-2-Norbornene) and Grubbs catalyst (1st generation) (on epoxy substrate) at low temperature (-50C). But it does not seem to work. I figured out that Grubbs catalyst (1st generation) is not very active at low temperature for ROMP.

Can you suggest any catalyst which will be active at very low temperature to proceed ROMP reaction with the system above.

I will much appreciate any suggestion.

Thanks.

17 Daryl Allen May 28, 2014 at 12:12 pm

Mohammad,
My first thought would be to try one of the fast initiating catalysts to see if you get any polymerization at that low temperature. The Grubbs group have published a bis-pyridine catalyst (Sanford, Love, Grubbs; Organometallilcs, 2001, 5314-5318) and the Wagener group a bis-3-Br-pyridine catalyst (Lehman Jr., Wagener; Organometallics, 2005, 1477-1482) that would be a place to start. Both complexes are prepared easily from the 2nd Generation Grubbs catalyst. Good luck!

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