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Professor W. Wulff Personal Research Biography

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I grew up on a dairy farm in northern Wisconsin (near Wulff valley).  I first became interested in chemistry one day when my father was feeding the pigs.  In order to prevent problems with  intestinal worms, copper sulfate was added to their feed.  I was enamored with the beautiful blue crystals that he was sprinkling in the feed tray and asked what it was.  I was only about eight and thus the answer “copper sulfate” was no more than a strange alien name, but somehow I got the impression that its name meant something about why it was blue.  My father gave me a few crystals to keep and the next Christmas, a chemistry set.  I was hooked.  Also about the same time I decided that I had to be a Professor at a University since the new medium of television portrayed chemistry as a highly noble and respected profession (Sputnik had an enormous positive effect on science in general in the late fifties and sixties).  The important lessons about how to be a successful scientist I would think are usually learned the

hard way.  In my case they certainly were.  These lessons also of course could not be learned without dedicated teachers that one encounters along the way.  My High School Chemistry teacher, Mr. Schwartz, was actually a biologist filling in because of a retirement.  Although he did not know a lot of chemistry, he was dedicated to helping students learn.  He once picked me up at 4:00 AM and drove me across the state for a High School Chemistry fair.  I had prepared a talk on an experiment that I had repeated from a Chemistry book.  I was embarrassed to find that everyone else’s talk involved original experiments.  The lesson learned from this is that science is about doing something new.  

 to topThe next important lesson came as an undergraduate at the University of Wisconsin at Eau Claire.  As a freshman, I was recruited to do research with Dr. Larry Schnack.  He was interested in the cyclopropyl carbinyl cation problem having received his Ph. D. with Charles DePuy.  We planned a detailed Hammet study of a number of substituted cyclopropyl carbinyl tosylates, which took me the next three years to do.  In my second year Dr. Schnack moved into administration but I continued the project.  He was too eventually become Chancellor of the University, a position he served with great distinction for almost two decades.  In my four years as an undergraduate I made a lot of compounds and measured a lot of rate constants.  In my senior year we assembled all the data for publication when much to my horror we discovered that Ken Wiberg at Yale published the same study with the same compounds.  The only consultation was that our rate constants matched his.  There was no point to publish our work.  The lesson learned here is that having a good idea is not enough, you have to do it and do it before anybody else does. 

 to topHaving batted zero for my professional career up to this point, I was ready for graduate school.  However, the United States Military had other plans for me at this time. Due to an unfortunately low draw in the lottery, I was forced into military service and served in the US Army for three years at Fort Meade Maryland. I work in a reference medical laboratory that serviced all branches of the armed services on the east coast. We did tests ranging from simple cholesterol and triglycerides to toxicological studies of drug overdoses. The latter was important because if an active military personnel died of a drug overdose, then the family would be denied all benefits. The most important event to occur during this time was the meeting of the woman who was to become my wife. Mary and I met on a blind date arranged by someone we knew who worked with me on a moon-lighting job at a local hospital. Mary's support of my goals in academia is the biggest factor responsible for the success I have had in my professional career.

to topI thought it was exceedingly kind of the Department of Chemistry at Iowa State University to hold open my graduate position until I finished my  military service. In July of 1974, I enrolled at Iowa State University and was fortunate enough to work for Professor Thomas Barton who was a truly inspirational scientist and personality.  His wit was faster than a speeding bullet and he had endless capacity to produce great ideas.  He liked risky projects and was a master at mechanistic deduction.  I tackled a flurry of high-risk ideas in my first three and a half years in graduate school but nothing worked.  Everything in my thesis comes from the last seven months in the lab.  Nonetheless, since we had several projects that all worked at once, we ended up with eight publications together on the study of organosilicon reactive intermediates including silanones, silylenes, silenes and disilenes.  This was an incredibly intense seven months during which I did not sleep more that five hours a night.  I finally found out what doing good science was.  It was an exhilarating and joyful period.  I will always be indebted to Thomas Barton for showing me how to do science right.  It is a debt that I can never repay, but showing new graduate students the joy of chemical research is at least a small effort in this regard not to mention a lot of fun.  

to topAlthough not a synthetic chemist, Professor Barton is at least partly responsible for my career in synthetic chemistry.  He did not like synthetic chemistry and forbade anyone in his lab from pursuing any leads that would have any possible applications in synthetic organic chemistry.  Synthetic chemistry was thus the forbidden fruit of which I was not allowed to partake and it had for me the allure of the unknown.  My decision to pursue a career in synthetic organic chemistry was cemented upon taking an organometallic course with Professor Robert Angelici and when Peter Vollhardt’s synthesis of estrone with organocobalt chemistry was published in the Journal of the American Chemical Society in 1979.  Professor Angelici’s course was so well done and properly suited for those who were not inorganic majors that everyone in the course came away with a real and profound sense that they could do organometallic chemistry.  Professor Vollhardt’s one-pot synthesis of estrone was a great inspiration to many a young chemist at the time since it seemed to crystallize a sense of what the power of the burgeoning new field of organometallics in organic synthesis could do. 

 to topThe field of organometallics in organic synthesis was just taking off when I was finishing grad school I was fortunate enough to land a postdoctoral position with one of the pioneers of the field, Martin Semmelhack at Princeton.  He had spent a decade or so exploring the scope and applications to organic synthesis of nucleophilic additions to arene chromium tricarbonyl complexes.  His charge to me was to explore the same reactions of naphthalene chromium tricarbonyl complexes and apply this to a total synthesis.  A number of these compounds were known, but their preparation usually gave mixtures of regioisomers with unsymmetrical naphthalenes having two benzene rings of different substitution patterns.  In preparation for writing my thesis, I decided that I needed to read the entire Journal of Organometallic Chemistry since at the time all the most important organosilicon papers were to be found in that Journal, along with JACS.  Much to my amazement, I came across a paper describing the selective formation of a naphthalene chromium tricarbonyl complex from the reaction of an aryl chromium carbene complex with an acetylene.  This reaction comprised the key step of a total synthesis deoxyfrenolicin that I proposed in an NIH postdoctoral fellowship application which was funded.  It was also pleasing to see the total synthesis appear in the literature two years after I finished my postdoctoral stay which was due to the talented efforts of four colleaques in the Semmelhack group.  

to top In the Fall of 1980 I accepted my first academic position as Assistant Professor at the University of Chicago.  I will never forget the first time I sat in my own lab and put my feet up on the desk.  The thought still gives me goose-bumps.  All of the projects that we started at Chicago involved the reactions of Fischer carbene complexes and their applications in organic synthesis.  My mentor, Martin Semmelhack, was kind enough to allow me to pursue this area on my own since I had brought the idea to his group.  This gesture was greatly appreciated and vital to establishing my own career.  This was an area that was ripe since a large number of reactions of Fischer carbene complexes with potential in organic synthesis had been discovered by inorganic chemists but synthetic organic chemists had not yet began working in the area.  My only competition when I started was Karl Heinz Dötz in Munich who had discovered the benzannulation reaction with alkynes.  In the US, Charles Casey at Wisconsin had done some early work put had stopped just before I began.  It was a great opportunity for us and it kept us so busy that we had no time to pursue any other ideas.  To get a sense of how rapidly this area was to grow from that point on one can look at a textbook of the time.  The first edition of “Principles and Applications of Organotransition Metal Chemistry” by Collman and Hegedus was published in 1980 and it tersely concludes that Fischer carbene complexes “are of little use in organic synthesis”.  The second edition appeared in 1986 and had an entire chapter devoted to the subject.  We have continued to work in the area and there are now dozens of groups around the world that have made contributions to the field.  Thirty-nine years after their discovery, Fischer carbene complexes are clearly one of the most important organometallic reagents in synthetic organic chemistry.  We have just recently completed a comprehensive review on the reaction of Fischer carbene complexes with alkynes.  For just this reaction alone, all of the known examples were assembled to give a Table that is over 600 pages long.  

to topJust as actors often get typecast into certain roles, chemists can become pigeonholed into defined fields and even sub-fields.  In the early nineties we began to work in an area of catalytic asymmetric synthesis, an area that was completely new for us.  With no track record in the area, we found that people were reluctant to open doors for us.  We have been pummeled mercilously by reviewers for the last six years trying to get this work funded.  We thus realized that we would have to get this program off the ground by subversive means, using funds from other grants as seed money.   This can only be done for so long since in the long run it can jeopardize existing programs.  We had pushed this about as far as we could at the University of Chicago and probably would not have been able to continue this program if we had not moved to Michigan State University.  The move here provided the funds necessary to move this program forward to the point where just recently we have obtained independent funding from the NIH to continue this program.  It wasn’t until we had solved a problem that no one else could solve that we were accepted into the catalytic asymmetric community.   While many methods have been developed over the years for the catalytic asymmetric synthesis of epoxides, related methods for the preparation of aziridines provided more elusive.  In the last 2-3 years we have developed the first general catalytic asymmetric synthesis of aziridines and now are beginning to be accepted as an established group in the field of catalytic asymmetric synthesis.  In the future we will examine catalyst designs for other important reactions in organic synthesis.  

 to topThe research group is now at eighteen members and is flourishing here at Michigan State University in both the areas of Fischer carbene complexes in organic synthesis and in catalytic asymmetric synthesis.  My family and I enjoy living in the East Lansing area and are glad that we made the move.  I like to take advantage of the summer and play tennis (when it’s not raining) and in the winters I like to drink wine (when it’s not raining).  

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