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E N O A E S S S L T A E A C R C I N S M S E E H C C TI N O CA February 2010 Vol. LXXXVIII, No. 6 N • AMERI

Monthly Meeting Summer Scholar Report NESACS Town Hall Meeting at Novartis By Danielle Raad and Dr. Theodore Betley

Joanne Stubbe 8th Annual Environmental An Interview by Mindy Levine Research Symposium Stubbe as “pretty inspiring” and “very twist due to the second fluorine,” said Joanne emotional.” Professor Stubbe. “Why it works on cancer cells specifically is related to Impact on Career Stubbe complex metabolism, and is something Despite the importance of the award, no one could have predicted a priori.” An Interview by Mindy Levine Professor Stubbe does not anticipate Professor Stubbe said that there that it will significantly impact her are relatively few scientists interested When Joanne Stubbe, Novartis Profes- career. “Awards can sometimes give in detailed enzymatic mechanisms sor of Chemistry and Biology at MIT, you visibility so you can attract better today. “People today think they can received a phone call late one night in people,” said Professor Stubbe. How- look at a protein crystal structure and September, she did not expect to hear ever, at a high-profile institution like know how things work - and they John Holdren, President Barack MIT, such added visibility may be less don’t have a clue. This is what we are Obama’s science and technology advi- important. up against.” sor, on the line. Nor did she anticipate “In the long run, is the award the Nonetheless, people can still be that he was calling to inform her that key thing?” Professor Stubbe asked successful in this research area as long she had won the National Medal of rhetorically. “Not really. The key thing as they are willing to continually learn Science, the highest domestic scientific is solving the problems.” new things, which is good advice for honor. “It came as a complete sur- all chemists in today’s rapidly chang- prise,” Professor Stubbe said. “I had no Research Activities ing world, Professor Stubbe said. idea.” Professor Stubbe’s research focuses on Mechanistic biochemical research Professor Stubbe, together with mechanistic investigations of biochem- remains an active and exciting research the 8 other National Medal winners, ical pathways involved in nucleotide area, she said, because “there are a lot received her award from President metabolism. This research has led to a of problems left to solve.” Obama in a ceremony on October 7, number of successful applications, 2009. One of the best parts of receiv- including the mechanism-based anti- Importance of Teaching ing the award, explained Professor cancer drug Gemcitabine, which is Despite such impressive research Stubbe, was that “my family finally patented and distributed by Eli Lilly achievements, Professor Stubbe stated figured out that what I do is impor- and Company. “The evidence is really categorically, “I think my most impor- tant.” Nine of her family members strong that Gemcitabine works like tant contributions have not been to were in Washington to witness the other mechanism-based inhibitors we research but to teaching.” She said ceremony, characterized by Professor have studied in detail with an unusual continued on page 12

2 The Nucleus February 2010 The Northeastern Section of the American Chemical Society, Inc. Contents Office: Marilou Cashman, 23 Cottage St., Natick, MA 01360. 1-800-872-2054 Joanne Stubbe 2 (Voice or FAX) or 508-653-6329. ______e-mail: mcash0953(at)aol.com An Interview by Mindy Levine Any Section business may be conducted via the business office above. Stephen Buchwald to Receive 2010 Esselen Award 4 NESACS Homepage: ______http://www.NESACS.org National Recognition for NESACS Student Chapters 4 David Cunningham, Webmaster ______ACS Hotline, Washington, D.C.: Monthly Meeting 5 1-800-227-5558 ______Officers 2010 Panel discussion at Novartis Institutes for Biochemical Research: ACS Town Chair: Hall Meeting-“The Prospects for Chemistry in the Future US Economy.” John McKew The 8th Annual Undergraduate Environmental Research Wyeth Research 200 Cambridge Park Drive Symposium at Bridgewater State College 6 Cambridge, MA 02140 ______617-665-5603; jmckew(at)wyeth.com Announcement 6 Chair-Elect: ______Patrick M. Gordon Sixteenth Annual Northeastern Section Undergraduate 1 Brae Circle Day to be held at UMass Boston. Woburn, MA 01801 gordonpat(at)emmanuel.edu February Historical Events in Chemistry 7 Immediate Past Chair: ______Dr. E. Joseph Billo By Leopold May 13 Shattuck Street Call for Nominations 8,9 Natick, MA 01760 ______508-653-3074, joseph.billo(at)verizon.net 2010 Northeast Region and ACS Awards Secretary: Michael Singer Summer Scholar Report 10 Sigma-Aldrich ______3 Strathmore Rd, Natick, MA 01360 Complexes with transition metal-to-oxo multiple bonds stabilizedBy pyrrole- 508-651-8151 X291, msinger(at)sial.com based ligands to target C-H bond functionalization. ByDanielle Raad, Brown Treasurer: Universtiy and Dr. Theodore Betley, Harvard University. James Piper 19 Mill Rd, Harvard, MA 01451 Cover: 978-456-3155, piper28(at)attglobal.net Pictured (R-L) are Jason MacLean, Christopher Cepero and Jonathan Auditor: Vitrano of Bridgewater State College in front of their poster, “Use of Portable Anthony Rosner XRF to Compare Arsenic Levels at the Surface of Wooden Play Structures.” They Archivist: were mentored by Dr. Cielito King. Their poster was presented at the 8th Annual Myron S. Simon 20 Somerset Rd, Newton, MA 02465 Undergraduate Environmental Research Symposium at Bridgewater State. 617-332-5273, romysimon(at)mindspring.com (Photo courtesy of David Wilson, BSC Office of Institutional Communications). Trustees: Deadlines: Peter C. Meltzer, Esther A. H. Hopkins, April 2010 Issue: February 10, 2010 Michael E. Strem May 2010 Issue: March 11, 2010 Councilors Alternate Councilors Term Ends 12/31/2010 Thomas R. Gilbert Timothy B. Frigo Pamela Nagafuji Mark Froimowitz Robert Lichter David Cunnigham Michael Singer Mukund Chorghade The Nucleus is published monthly, except June and August, by the Northeastern Section of the American Term Ends 12/31/2011 Chemical Society, Inc. Forms close for advertising on the 1st of the month of the preceding issue. Text Doris I. Lewis C. Jaworek-Lopes must be received by the editor six weeks before the date of issue. Mary Burgess Patrick M. Gordon Editor: Michael P. Filosa, Ph.D., ZINK Imaging, Inc., 16 Crosby Drive, Building 4G, Morton Z. Hoffman Lawrence Scott Michael P. Filosa Donald Rickter Bedford, MA 01730 Email: Michael.filosa(at)zink.com; Tel: 508-843-9070 Kathi Brown Liming Shao Associate Editors: Myron S. Simon, 20 Somerset Rd., W. Newton, MA 02465, Tel: 617-332-5273, Term Ends 12/31/2012 Sheila E Rodman, Konarka Technologies, Inc., 116 John St. Suite 12, Lowell, Amy E. Tapper Michaeline F. Chen MA 01852 Email: srodman(at)konarka.com tel 978-569-1414, Catherine E. Costello Jerry P. Jasinski Mindy Levine, 516-697-9688 (c), 617-258-6536(w), mindy.levine(at)gmail.com Patricia A. Mabrouk Gary R. Weisman Assistant Editors: Stefan G. Koenig, Sonia Taktak Dorothy J. Phillips Marietta Schwartz Board of Publications: Vivian K. Walworth (Chair), David Cunningham, Mary Mahaney Ruth Tanner Norton P. Peet Business Manager: Karen Piper, 19 Mill Rd., Harvard, MA 01451, Tel: 978-456-8622 All Chairs of standing Advertising Manager: Vincent J. Gale, P.O. Box 1150, Marshfield, MA 02050, Committees, the editor Email: [email protected]; Tel: 781-837-0424 of THE NUCLEUS, and Contributing Editors: Morton Hoffman, Feature Editor; Dennis Sardella, Book Reviews the Trustees of Section Calendar Coordinator: Sheila Rodman, email: srodman(at)konarka.com Funds are members of the Photographers: Morton Z. Hoffman and James Phillips Board of Directors. Any Proofreaders: Donald O. Rickter, Vivian K. Walworth, Mindy Levine Councilor of the American Chemical Society residing within the section area is an ex officio Webmaster: David Cunningham, webmaster(at)nesacs.org member of the Board of Directors. Copyright 2009, Northeastern Section of the American Chemical Society, Inc. The Nucleus February 2010 3 Buchwald National Corporate Patrons ($2000+) Abbott Bioresearch Genzyme to Receive Recognition Lyophilization Service of New England Merck 2010 for NESACS Novartis Institute for Biochemical Research Schering Corporation Esselen Student Sepracor Serono Reproductive Institute Vertex Pharmaceuticals Award Chapters Wyeth Pharmaceuticals The ACS Committee on Education has Patrons ($1000-$1999) selected the following student chapters Aptuit in the Northeastern Section to receive Broad Institute special recognition for the programs Creagen Biosciences and activities described in their 2008- Estate of Wallace Gleekman 2009 reports: Irix Pharmaceuticals Outstanding Recognition PCI Synthesis Northeastern University, Boston, MA; Shasun USA Andrea Lebed, chapter president; Prof. Sirtris Pharmaceuticals Jordan Swift, faculty advisor. Strem Chemicals Donors ($300-$999) Stephen L. Buchwald, Camille Dreyfus Commendable Recognition Professor of Chemistry at the Massa- Stonehill College, North Easton, MA; Cambridge-Major Laboratories chusetts Institute of Technology (MIT), Natalie Dogal, chapter president; Prof. Medicilon Inc has been selected to receive the 2010 Cheryl Schnitzer and Prof. Marilena Organix Gustavus J. Esselen Award for Chem- Hall, faculty advisors Peptech Corp SAPA-NE istry in the Public Interest from the Suffolk University, Boston, MA; Northeastern Section of the American Urjana Porcei, chapter president; Prof. Chemical Society (NESACS). Doris Lewis, faculty advisor. The Esselen Award is presented Summer Scholar annually to recognize and reward a Honorable Mention U.S. or Canadian chemist whose scien- Keene State College, Keene, NH; Continued from page 11 tific and technical work has con- Joseph Meany, chapter president; Prof. Refer ences tributed to the public well-being and Colin Abernethy and Prof. Denise 1. Labinger, J.A.; Bercaw, J.E. Nature Junge, faculty advisors has thereby communicated positive th 2002, 417, 507-514. values of the chemical profession. Pro- They will be honored at the 239 2. Bergman, R.G. Organometall. Chem. fessor Buchwald’s selection recognizes ACS National Chemistry Meeting in 2007, 446, 391-393. San Francisco, CA, on Sunday, March 3. Chen, M.S.; White, M.S. Science his major impact on medicinal chem- N istry, due to his development of palla- 21, 2010. 2007, 318, 783-787. dium and copper catalyzed processes 4. Godula, K.; Sames, D. Science 2006, to form carbon-nitrogen and carbon- 312, 67-72. toral work at the California Institute of 5. Badiei, Y.M.; Dinescu, A.; Dai, X.; oxygen bonds. These catalysts are used Technology. He earned a B.S. in chem- Palomini, R.M.; Heinemann, F.W.; daily by the discovery groups of nearly istry at Brown University in 1977, and Cundari, T.R.; Warren, T.H. Angew. every major pharmaceutical company an A.M. (1980) and a Ph.D. (1982) in Chem. Int. Ed. 2008, 47, 9961-9964. worldwide. His catalysts have enabled chemistry from Harvard University. He 6. King, E.R.; Betley, T.A. Inorg. Chem. the synthesis of novel, promising, has previously received the ACS 2009, 48, 2361-2363. small molecule drugs targeting a very Award in Organometallic Chemistry in 7. Davies, H.M.L.; Manning, J.R. Nature wide range of diseases. His catalysts 2000 and the ACS Award for Creative 2008, 451, 417-424. have also been instrumental in devel- Work in Synthetic Organic Chemistry 8. Benson, D.E.; Suslick, K.S.; Sligar, S. oping novel organic semi-conductors in 2006. G. Biochem. 1997, 36, 5104-5107. and in a wide range of other non- Professor Buchwald will receive 9. Rieth, R.D.; Mankad, N.P.; Calimano, medicinal chemical syntheses. the Esselen Award medal and a $5000 E.; Sadighi, J.P. Org. Lett. 2004, 6, Professor Buchwald joined the prize at the Esselen award dinner and 3981-3983. MIT Department of Chemistry in 1984 lecture at Harvard University on 10. Engel, N.; Steglich, W. Angew. Chem. N N as an assistant professor after post-doc- Thursday, April 8, 2010. Int. Ed. 1978, 9, 676. 4 The Nucleus February 2010 February Monthly Meeting Meeting The 903rd Meeting of the Northeastern Section of the American Chemical Society Genesis of a Town Hall Thursday – February 18, 2010 Forum: Reasons to Attend a Novartis Institutes for Biomedical Research NESACS Monthly Meeting 250 Massachusetts Ave, Cambridge, MA 02139 By Leland Johnson 2:30 pm Board Meeting About a year ago, January 15th, to be exact, I walked in early and picked an 4:00-6:00 pm Panel Discussion empty chair amongst a sea of empty Northeastern Section ACS (NESACS) Town Hall Meeting— place settings near the back of Whitney “The Prospects for Chemistry in the Future US Economy” Hall B, Holiday Inn in Brookline. It was the night of the Monthly Meeting • Julian Adams, panelist, President and CSO of Infinity Pharmaceuticals for NESACS, and as the YCC Chair at • Chris Austin, panelist, Director of the NIH Chemical Genomics Center that time, I attended the NESACS • Scott Biller, moderator, VP of Global Discovery Chemistry, Novartis board meetings, social hour, and an Institutes for Biomedical Research occasional dinner in order to meet with colleagues, make new connections, and • Joe Francisco, panelist, ACS President for 2010, Purdue University listen to as much of the program as I • Robert Langer, panelist, Institute Professor and entrepreneur, Massa- could before heading home to help put chusetts Institute of Technology my little guy to sleep for the night. • Jordan Swift, panelist, Co-Op Education Coordinator, Northeastern I put my coat on the back of the University Chemistry Department chair and a cloth napkin on my seat, and I headed back out into the function 6:00-7:00 pm Reception lobby for the social hour. After catching up with several colleagues from indus- ADVANCED REGISTRATION IS REQUIRED. try, volunteers for NESACS and those Registration details will be on the front page at www.nesacs.org. If you have any who were working on the NESACS- questions, please contact Leland Johnson at [email protected] or ljohn- GDCh German Exchange Program, I [email protected] returned with the masses to find nearly Directions: From the Massachusetts Turnpike: Take exit 18 toward all of the seats occupied with section Brighton/Cambridge. Keep right at the fork to continue toward Cambridge St members, ACS scholars, NESACS and merge onto Cambridge St. Continue onto River St/River St Bridge. Con- board members, and other guests. tinue to follow River St. for 0.8 mi to Central Square. Turn right at Massachu- I was happy to find that my efforts setts Ave. Destination will be on the right in 0.5 mi. to reserve a seat had succeeded, and there happened to be one last available Parking: Shaw’s (Star) Supermarket parking garage, using the entrance on seat directly to my left. A few minutes Franklin or Green Streets. later, I introduced myself to Professor By Public Transportation: Take the MBTA Red line to the Central Square stop Joe Francisco as he sat down in the and proceed to 250 Massachusetts Ave. seat next to me. This was a pleasant surprise and, as it turned out, a stroke of luck. As the dinner progressed, table members engaged Joe and one another, New Members and the conversation flowed around the table. Invitation to attend a meeting I talked with Joe for several min- You are cordially invited to attend one Thursday of the month, letting her utes about the economy, prospects for N of our upcoming Section meetings as a know that you are a new member. chemistry, and my family. As the local guest of the Section at the social hour YCC chair, I mentioned that several of and dinner preceding the meeting. What exactly goes on at NESACS’ my colleagues from various pharma- Please call Marilou Cashman at monthly Board meetings? ceutical and biotechnology companies 800-872-2054, 508-653-6329 or: www.nesacs.org/reports in the area had missed the opportunity Mcash(at)aol.com by noon of the first to talk with him during his stay. Continued on page 12

The Nucleus February 2010 5 The 8th Annual Announcement The Sixteenth Annual Undergraduate Northeastern Section Environmental Research Undergraduate Day Saturday, February 27th, 2010 Hosted by the Department of Chem- Symposium at istry, UMass Boston Sponsored by the Northeastern Section Bridgewater State College of the American Chemical Society 9:00 Registration (Directions at On Saturday, November 14, 2009, the th http://www.umb.edu/parking_ 8 Annual Undergraduate Environ- transport/directions.html; park mental Research Symposium was held in the North Lot, Campus Cen- in the John Joseph Moakley Center at ter; come into the Campus Cen- Bridgewater State College. The Sym- ter and follow the signs to the posium was sponsored by Bridgewater registration desk) State College, their Office of Under- graduate Research and Center for Sus- 9:30 Welcoming Remarks tainability, and by NESACS. 9:45 Keynote Address – Berkeley W. The Symposium ran from 9:00 Cue, Vice President, Pharma- AM to 2:30 PM and featured a record ceutical Sciences, Pfizer Global 58 poster presentations from under- R&D (retired) graduate researchers, and was attended 10:30 Coffee Break by over 140 students, faculty and Guest speaker Dr. Carl Lamborg, Department of guests representing eleven public and Marine Chemistry and Geochemistry, Woods 10:45 Research Talks (choose one) private colleges and universities in Hole Oceanographic Institution, "Research into 12:00 Lunch New England. Attendees were treated the Biogeochemistry of Mercury in the Ocean and its Impact on Public Policy" 12:30 Resume Review and Graduate to a continental breakfast and lunch. School/Industry Fair The Symposium was officially opened by Dr. Howard London, 1:30 Panel Discussions (choose one): Provost and Vice-President for Aca- 1. Choosing and Applying to a demic affairs at Bridgewater State Col- Graduate School lege. Dr. London praised the students 2. Careers in Chemistry without for their work confronting urgent envi- a Graduate Degree ronmental issues, and fashioning 2:15 Adjournment acceptable and effective solutions. He congratulated the students on their There will be a $10 registration fee to work and also expressed his thanks to partially cover the cost of coffee and the faculty mentors who provided lunch, which will be provided. If you guidance and support. would like more information, or if Student researchers from Plymouth State Uni- The theme of the 2009 Sympo- versity present their work, L-R: Kris Wojtusik, your school or company would like to sium was “Environmental Analysis.” Rebecca Mailhot, and Ben Crawford, “Habitat send a representative to the Graduate The formal program began at 9:30 AM preference of crayfish (Orconectes virilis) School and Industry Fair, please with a presentation by Dr. Carl Lam- among three different macrophytes” contact Marietta Schwartz – mari- (Photos by David Wilson) [email protected]; phone 617- borg from the Department of Marine N Chemistry and Geochemistry at Woods The complete program with all 287-6146; fax 617-287-6030. Hole Oceanographic Institution. Dr. presenters, titles and abstracts can be Lamborg’s talk was entitled, accessed from the symposium web “Research into the Biogeochemistry of page: http://www.bridgew.edu/En Mercury in the Ocean and its Impact vironmental/ on Public Policy.” The 9th Annual Environmental The poster sessions began imme- Research Symposium is tentatively diately following the presentation, run- scheduled for Saturday, November 13, N ning from 10:45AM – 2:15PM. 2010.

6 The Nucleus February 2010 February Historical Events in Chemistry by Leopold May, The Catholic University of America, Washington, DC February 3, 1893 devised a formula for measuring the was born on this date. In 1998, he Lenora Neuffer Bilger, a researcher heat value of fuels (DuLong For- shared the Nobel Prize in Chemistry in asymmetric nitrogen compounds, mula). with Johann Diesenhofer and Hart- was born on this date. She also mut Michel for the determination of February 14, 1917 received the Garvan Medal from the three-dimensional structure of a Twenty-five years ago in 1985, Her- ACS in 1953. photosynthetic reaction centre. bert A. Hauptman and Jerome Karle February 5, 1840 shared the Nobel Prize in Chemistry February 24, 1913 John Boyd Dunlop, who developed for their outstanding achievements William S. Johnson devised new and pneumatic rubber tires, was born on in the development of direct meth- efficient methods to synthesize com- this date. ods for the determination of crystal plex molecules including corticoid structures. Herbert A. Hauptman steroids. He was born on this date. February 6, 1860 was born on this date. One hundred and fifty years ago, February 25, 1869 Nikolai D. Zelinsky, was born on February 18, 1745 Phoebus A. T. Levene, who was this date. He researched on the catal- Alessandro G. A. A. Volta, who was born on this date, was a researcher ysis of disproportion at ion reactions born on this date, invented the on the biochemistry of proteins. of hydrocarbons and the bromina- voltaic pile, volta pila, and observed February 26, 1905 tion of fatty acids (Hell-Volhard- the bubbling of methane in swamps. Zelinsky reaction). He developed a gas lantern that was William J. Sparks, an innovator and electrically ignited. The unit of developer in synthetic rubber, was February 7, 1850 electric potential, the volt, is named born on this date. John B. F. Herreshoff, who devel- in his honor. Additional historical events can be oped a method for manufacturing found at Dr. May’s website: February 20, 1937 sulfuric acid, was born on this date. http://faculty.cua.edu/may/Chemistr Robert Huber, who did research on N February 8, 1777 ycalendar.htm.. the three-dimensional structure of Bernard Courtois, who was born on proteins involved in photosynthesis, this day, discovered iodine in the liquor from the lixiviation of kelp in 1811. February 8, 1866 Moses Gomberg, who synthesized the first stable free radical (triph- enyl-methyl), was born on this date. He also did research on tau- tomerism. February 11, 1847 Thomas A. Edison was an inventor who invented the incandescent lamp and the mimeograph. He was born on this date. February 12, 1785 Two hundred and twenty-five years ago, Pierre L. DuLong was born on this date. He discovered nitrogen tri- chloride in 1813; and was a researcher on refractive indices and specific heats of gases. In 1819, he and Aléxis Thérèse Petit discovered the law of constancy of atomic heat and suggested that acids were com- pounds of hydrogen in 1815. He

The Nucleus February 2010 7 Northeast Region of the American Chemical Society, Inc. CALL FOR NOMINATIONS FOR THE 2010 NORTHEAST REGION AND ACS AWARDS Northeast Region Awards for 2010 • THE ACS DIVISION OF CHEMICAL EDUCATION NORTHEAST REGION AWARD FOR EXCELLENCE IN HIGH SCHOOL TEACHING • THE E. ANN NALLEY REGIONAL AWARD FOR VOLUNTEER SERVICE TO THE AMERICAN CHEMICAL SOCIETY • THE ACS REGIONAL INDUSTRIAL INNOVATION AWARDS • THE NORTHEAST REGION, ACS AWARD FOR ACHIEVEMENTS IN THE CHEMICAL SCIENCES The deadline for these awards is April 15, 2010

Award offered by the National ACS THE STANLEY C. ISRAEL REGIONAL AWARD FOR ADVANCING DIVERSITY IN THE CHEMICAL SCIENCES The deadline for this award is March 1, 2010

Presentation of awards: The awards will be presented at the 2010 Northeast Regional Meeting (NERM) Potsdam, New York June 2 – 5, 2010

Specifics about each award and nomination forms may be found on the webpage for the 2010 Northeast Regional Meeting (NERM)

www.nerm2010.org

8 The Nucleus February 2010 creative innovations have contributed regional meeting at which the award Call for to the commercial success of their will be presented. company and, consequently, to the Eligibility: Nominees may come from Nominations good of the community and society. academia, industry, government, or Eligibility: Nominee must be a chemi- independent entities, and may also be Awards of the Northeast cal professional and an ACS member. organizations, including ACS local For team nominations, only one mem- sections and divisions. The nominee Region of the American ber needs to be an ACS member. must have created and fostered ongo- Chemical Society Those who are not ACS members, but ing programs or activities that result in All awards will be presented at the are employed by an ACS Corporation increased numbers of persons from 2010 Northeast Regional Meeting Associates Member Company, qualify diverse and underrepresented minority (NERM) June 2nd – 5th, 2010, Pots- for nomination. groups, persons with disabilities, or dam, New York women that participate in the chemical THE NORTHEAST REGION, ACS enterprise. THE ACS DIVISION OF CHEMI- AWARD FOR ACHIEVEMENTS CAL EDUCATION NORTHEAST IN THE CHEMICAL SCIENCES The Nomination Package must REGION AWARD FOR EXCEL- Purpose: To recognize notably out- include: LENCE IN HIGH SCHOOL standing achievements by a chemist in • A letter of nomination TEACHING the Northeast Region. The award is • A CV or resume containing relevant Purpose: To recognize, encourage, conferred annually on a scientist who diversity-promotion activities and and stimulate outstanding teachers of has made meritorious research contri- factual data on outcomes. high school chemistry in the Northeast butions leading to the advancement of pure or applied chemistry. • At least one, but no more than three Region. supportive letters, one of which must Eligibility: The nominee must be a Eligibility: The nominee must be come from the nominee’s ACS Local member of the ACS, residing in the actively engaged in the teaching of Section. Mailing address, phone Northeast Region and whose work, on chemistry or a chemical science in a number(s), and e-mail address of which the nomination is based, has high school (grades 9-12) on at least a nominee/supporter must be provided. half-time basis. been carried out during a period of res- idence in the area encompassing the Contact Information: THE E. ANN NALLEY Local Sections that comprise the American Chemical Society REGIONAL AWARD FOR VOL- Northeast Region. Department of Diversity Programs UNTEER SERVICE TO THE 1155 Sixteenth Street, NW The deadline for all of the above Washington, DC 20036 AMERICAN CHEMICAL SOCI- listed awards is April 15, 2010. ETY Fax: 202-776-8003 For most awards, a nomination form Email: [email protected] Purpose: To recognize the volunteer must be used. Please refer to the 2010 efforts of individuals who have served Deadline for receipt of nominations: NERM Website for all forms and other N the American Chemical Society by guidelines. www.nerm2010.org March 1, 2010. contributing significantly to the goals and objectives of the Society through THE STANLEY C. ISRAEL their Regional Activities. REGIONAL AWARD FOR What’s Yours? Eligibility: The nominee must be a ADVANCING DIVERSITY IN THE member of the ACS, residing in a CHEMICAL SCIENCES DMPK Scientist, Local Section within the Northeast Sponsor: ACS Committee on Minority LC/MS Product Specialist, Region, who has made significant con- Affairs Mass Spec Operator, tributions to the Section and Region of Purpose: The Stanley C. Israel Staff Investigator, the ACS. Regional Award recognizes individuals Process Chemist, THE ACS REGIONAL INDUS- and/or institutions that have advanced QA Manager, TRIAL INNOVATION AWARDS diversity in the chemical sciences and Synthetic Chemist, Purpose: To celebrate the successful significantly stimulated or fostered Lab Instructor . . . innovations of industrial chemists and activities that promote inclusiveness Many local employers post positions chemical engineers which contribute to within the region. The award consists on the NESACS job board. the health of their local and regional of a medal and a $1,000 grant to sup- economy and the corporate leadership port and further the activities for which Find yours at for its advancement of a healthy econ- the award was made. The award also www.nesacs.org/jobs omy. This award is given to an indi- will include funding to cover the recip- vidual or team of individuals whose ient’s travel expenses to the ACS

The Nucleus February 2010 9 Summer Scholar Report Complexes with transition metal-to-oxo multiple bonds stabilized by pyrrole-based ligands to target C-H bond functionalization Danielle Raad, Chemistry Department, Brown University, Providence, RI Dr. Theodore Betley, Department of Chemistry and Chemical Biology, Harvard University, Cambridge, MA Abstract nature; cytochrome P450 enzymes employ the use of an Complexes with high-valent metal-oxo multiple bonds are Fe=O intermediate to aid in the catalysis of C-H to C-O potential catalysts for the activation of typically inert C–H bonds of compounds in the human body.2,8 alkane bonds. We propose a group of transition metal com- Synthetic Methods plexes characterized by such metal to ligand multiple bonds, The initial step in building the catalyst complex is to and stabilized by tridentate pyrrole-based ligand platforms. assemble the ligand backbone. All manipulations were per- These tris(pyrrole)ethane, or TPE, ligands were prepared formed under inert atmosphere in a glove box, and heated synthetically with substituted pyrrole moieties, in particular reactions were carried out in air-tight bomb flasks in fume 2-mesityl pyrrole. These were subsequently deprotonated hoods. First, distilled pyrrole was carefully deprotonated and metallated, with the insertion of a transition metal coor- with sodium hydride. The resulting sodium pyrrolide was dinated to the three pyrrole nitrogens. Further steps include reacted with 2-bromomesitylene in the presence of a palla- oxidizing the metal center and producing metal-to-oxo mul- dium catalyst and zinc chloride to form 2-mesityl pyrrole tiple bonds stabilized by the TPE ligand. These reactive oxo, (Scheme 1), according to a previously reported procedure.9 and analogous imide, complexes may have the potential to The mixture was heated at 100°C for two days. This 2- activate inert C-H bonds and subsequently catalyze their functionalization. Scheme 1 Synthesis of 2-Mesityl pyrrole Background Saturated hydrocarbons are typically unreactive, and have been historically inert in all but the most extreme of reaction environments. At elevated temperatures, combus- tion occurs indiscriminately, yielding the industrially useless mesityl pyrrole was next reacted with trimethyl orthoacetate products of carbon dioxide and water. Established methods with the acid catalyst pyridinium p-toluene sulfonate to induce alkane reactivity include cracking, thermal dehy- (PPTS) at 70°C for one week (Scheme 2). The product is the drogenation, and exposure to highly reactive species, which stable tris(2-mesityl-pyrrole)ethane (TPE) tridentate ligand involve acute reaction conditions, are relatively expensive, structure. To prepare for metallation, it is deprotonated and and offer little control over product selectivity.1 Facile meth- lithiated. A reaction with phenyllithium at low temperatures ods for activation of these stable C-H bonds and conversion results in a lithium atom ligated to each of the three pyrrole of ubiquitous alkanes into synthetically useful compounds Scheme 2 could revolutionize the chemical industry, allowing the Synthesis of tris-pyrrole ethane(TPE) ligand exploitation of naturally found hydrocarbons as a previ- ously-untapped low-cost chemical feedstock.2 Practical insertion into the hydrocarbons of new bonds, such as C-C, C-O, or C-N, necessitates the use of effective transition metal catalysts, which are able to provide pre- dictable selectivity.3,4 Functionalization can occur without the need for intermediates or waste products, decreasing unpleasant environmental consequences while optimizing atom and energy efficiency.5 Several catalysts have been nitrogens, with a THF molecule in the other coordination thus far discovered with such functionalization abilities. A site (Scheme 3). Finally, with this ligand backbone, abbrevi- small-molecule iron catalyst has been shown to oxidize C-H ated (TPE)Li3, a series of metallation reactions were run bonds with hydrogen peroxide,3 while much research is with different ruthenium, nickel, and cobalt compounds focused on catalytic C-H amination, for example using cop- (Table 1), by mixing the two thawing reagents. 5 6 per or iron organometallic complexes. Results and Discussion Often, the chemical species capable of such direct intro- The synthesis of the TPE ligand resulted in pure mate- duction of a new functional group into a stable hydrocarbon 1 rial, although in sparse yields (10-20%). H NMR shifts bond is characterized by a metal-ligand multiple bond. Oxy- occurred at ∂ 7.33, 6.82, 6.16, 6.04, 2.19, 2.15, 1.81ppm gen, nitrogen, or carbon centers doubly or triply bound to (Figure 1). Though the TPE ligand was isolated in relatively late transition metals have been found to promote such 7 pure yields, when reacted with the different metal precursors transformations. This feature is successfully utilized by

10 The Nucleus February 2010 in the following reactions, it produced metallic complexes in Table 1 extremely low yields, or failed completely. An outline of the Summary of transmetallation experiments with lithiated different metallation reactions can be seen in table 1. Two TPE ligand ruthenium precursors were used, RuCl2(PPh3)3 and RuCl2(COD). Both of the preliminary reactions, run by warming frozen reactants up to room temperature and stir- ring for 2 hours yielded no reaction (1, 2). The conditions for the reaction with RuCl2(PPh3)3 were next altered to try to induce the reaction. Increasing the reaction time to 15 hours was unsuccessful (3). However, heating the reaction at 60°C for one day (4) produced small, unmeasurable amounts of a metallated ruthenium complex. Reaction of (TPE)Li3 with analogous nickel and cobalt compounds (5, 6) produced ments has mesityl groups located off the ∂ position of the compounds that go through a series of color changes as the pyrrole groups. Substituents with larger mesityl analogues, i t solvent is changed. This indicates ligand exchange with the such as 2,4,6-(R)3C6H2, where R is CF3, Pr, or Bu may also solvent molecules. The reaction with cobalt chloride be used, in addition to smaller molecules, such as the sim- afforded no measurable product (7). pler isopropyl pyrrole and tert-butyl pyrrole.10 These will Future Directions serve to sterically hinder the metal center around the C3- symmetric pocket of the ligand backbone, enough to prevent These preliminary tests show that it is possible to create the formation of dimers. Tuning the substitutents could pro- organometallic complexes by inserting transition metals into duce slightly different results in the next step of the catalyst the tridentate TPE ligand, with the appropriate reaction con- synthesis. ditions. Future work on this project involves tuning these The next step after metallation will be oxo transfer to conditions to induce clean and efficient metallation reac- establish a metal to oxygen bond. A variety of oxygen trans- tions. Once the metallated complexes are stabilized, crystal fer agents would be used, such as ONMe3, PhIO, O2, structures will be determined in order to elucidate the iden- O2CMe2, oxone, and H2O2 (Scheme 4). A similar group tity of the additional ligands on the metal, and the structure transfer reaction using amides will be performed to produce of the complex. the electrically analogous nitrene functionality. The specific ligand used in the aforementioned experi- Scheme 4 Scheme 3 Lithiation of TPE ligand

The oxidation state of the resulting complexes would be +4, equivalent to the reactive iron metal center of the cytochrome P450 enzyme. Once these complexes with tran- sition metals-to-oxo multiple bonds are stabilized, they will Figure 1 1 be characterized and compared. An attempt will also be HNMR of TPE Ligand made to oxidize them further; an oxidation state of +5 would increase their reactivity even more. Reactivity pro- files with various alkanes will be determined, so that the ability to activate or even functionalize C-H bonds may be probed. Hopefully, this research will continue and culminate in the production of a new class of complexes with unique reaction chemistry suitable for functionalizing alkanes, with the potential to drastically impact the field of organic syn- thesis. Acknowledgements Danielle Raad was funded by a Norris-Richards Sum- mer Research Scholarship, given by NESACS. She would like to thank the other members of the research group, and especially Graham Sazama for his invaluable mentorship and advice. continued on page 4

The Nucleus February 2010 11 Joanne Stubbe February Meeting December, we had merged the event with the February Monthly Meeting, Continued from page 2 Continued from page 5 and the schedule of events had been teaching can have a tremendous Around the time dessert was served, I set. impact. For example, if there are 25 had to confess to Joe that I would be The members of the panel, including students in a class, and 5 of those stu- unable to stay for his talk. As we Scott Biller as moderator, are: dents are inspired, each one can go on wrapped up our own discussion, I to make a major contribution to his or asked Joe to come back to Boston for • Julian Adams, President and CSO of her field. an open forum, inviting younger Infinity Pharmaceuticals Recently Professor Stubbe gave a chemists to attend for a discussion and • Chris Austin, Director of the NIH seminar at the University of South Car- a Q and A session. Chemical Genomics Center olina. While at the university, one of A few weeks later, I began the • Joseph Francisco, ACS President the faculty members approached her conversations with Alicia Harris and said that her class was the best (National ACS) regarding my invita- • Robert Langer, Institute Professor at class he had ever taken. “I may not tion to Joe. He accepted, and in August MIT and entrepreneur th even remember a particular student,” we secured the date, February 18 . As • Jordan Swift, Co-Op Education Professor Stubbe said, “but I think I the fall approached, it was time to Coordinator, Chemistry Department, am impacting the people who go into secure a location and a sponsor. I Northeastern University science.” emailed Scott Biller, VP of Global Dis- Gender Issues covery Chemistry at Novartis Institutes We are looking forward to a discussion for Biomedical Research (NIBR). of, “The Prospects for Chemistry in the “I don’t want to discuss this issue,” Within a few days, availability of Future US Economy.” Following intro- Professor Stubbe said when the ques- space at NIBR was confirmed, and ductory remarks and presentations tion of gender issues in chemistry was Scott informed me that Novartis would beginning at 4 PM, there will be a Q first raised, “even though I think it is a sponsor the event. Shortly thereafter, and A session with members of the very important one.” Nonetheless, as Scott, John McKew and I invited lead- audience. There will be a reception the first woman to be tenured in the ers from industry, government, and from 6 to 7 PM following the discus- MIT chemistry department, she is per- academia (many bridging at least two sion. This NESACS February Monthly haps in a unique position to comment of these areas) to join the panel. By Meeting is sponsored and hosted by . on the question Professor Stubbe has Novartis, and I wish to personally spent a lot of time helping young fac- thank Scott Biller and his team for ulty members, both men and women, tics. “Spend more time doing good sci- facilitating this anticipated event. The adjust to life at MIT. ence,” she said, and hopefully the good NESACS monthly meetings provide Professor Stubbe explained that science will be recognized appropri- great opportunities to network with there used to be discrimination against ately. Moreover, in Professor Stubbe’s colleagues, classmates, speakers lead- female academics of all disciplines, in opinion, the six-year period before ers in the chemical sciences. In retro- areas such as compensation and the tenure is really too short to make a spect, I encourage more NESACS tenure process. There has been tremen- substantial contribution, especially in members to attend our monthly meet- dous progress in reducing such dis- the biological sciences. ings. You can never tell who might sit crimination over the years, said Reflections on MIT next to you during dinner, and where Professor Stubbe, so that “women that might lead. Networking is clearly coming in the present generation may When asked to reflect on her career at MIT, Professor Stubbe said, “My a huge part of monthly meetings, and not even realize how much energy we encourage you to paricipate. went into changing the culture.” career wouldn’t be what it is at all without being at MIT. Being here has Advanced reservations are required Advice about Academia allowed me to set up outstanding col- and space is limited. To inquire about Professor Stubbe explained some laborations, which has enabled me to availability, please contact Leland L. advantages to choosing a career in aca- do science that I otherwise couldn’t Johnson, Jr., ljohnson@creagenbio. demia. “A big plus for academics is have done. At MIT, there are so many com. that you can work on something that people interested in science that if you you are really passionate about,” said use your energy wisely you can do just The meeting will be held at NIBR in Professor Stubbe. “For example, I have about anything. Being at MIT has Cambridge at the 250 Massachusetts been fortunate my whole life to be paid allowed me the privilege of working Avenue site. Parking will be at Shaw’s to do my hobby.” with the best graduate students in the (Star) Supermarket parking garage, using the entrance on Franklin or Professor Stubbe cautioned new country.” N faculty members against spending Professor Stubbe concluded, “It is Green Streets. excessive energy worrying about a tough place, but a very special N tenure decisions and departmental poli- place.”

12 The Nucleus February 2010 BUSINESS DIRECTORY SERVICES SERVICES SERVICES

The Nucleus February 2010 13 BUSINESS DIRECTORY SERVICES SERVICES SERVICES

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Feb 04 Feb 22 Calendar Karl Scheidt (Northwestern University) Anna Croft (Bangor University, UK) MIT, 6-120 MIT, 56-114 Check the NESACS home page 4:00 pm 4:00 pm for late Calendar additions: Feb 23 http://www.NESACS.org Max Diem (Northeastern University) “Micro-spectroscopy for Medical Diagnostics: Prof. Brad Smith (Notre Dame University) Infrared and Raman Microscopy of Human “Supramolecular probes for optical bioimaging” Note also the Chemistry Department web Cells” pages for travel directions and updates. Boston College, Merkert 130 Univ. New Hampshire, Iddles L103 4:00 pm These include: 11:10 am http://chemserv.bc.edu/seminar.html Feb 08 Feb 24 http://www.bu.edu/chemistry/events/ Elena Rybak-Akimova (Tufts University) http://www.chem.brandeis.edu/colloquium.shtml The Pfizer Symposium Harvard, Pfizer Lecture Hall http://www-chem.harvard.edu/events/ David MacMillan (Princeton University) 4:00 pm http://web.mit.edu/chemistry/ Harvard, Pfizer Lecture Hall www.chem.neu.edu/web/calendar/index.html 4:00 pm Feb 25 http://chem.tufts.edu/seminars.html [CHEM.] Feb 09 Judith Herzfeld (Brandeis University) http://ase.tufts.edu/chemical/seminar.htm Harvard, Pfizer Lecture Hall [CHEM. ENGG.] Prof. Daniel Raleigh (SUNY-Stony Brook) 4:00 pm http://www.chem.umb.edu/ Boston College, Merkert 130 www.umassd.edu/cas/chemistry/seminars.cfm 4:00 pm Notices for The Nucleus www.uml.edu/Dept/Chemistry/speakers.html Feb 10 http://www.unh.edu/chemistry/seminars.html Calendar of Seminars should Malcolm Chisholm (Ohio State University) be sent to: Feb 01 MIT, Room 6-120 Timothy F. Jamison (MIT) 4:00 pm Sheila E Rodman Brandeis University, Gerstenzang 122 Feb 16 Konarka Technologies, Inc. 3:45 pm 116 John St. Suite 12 Prof. Karl A. Scheidt (Northwestern University) Feb 02 “New Discoveries with Carbene Catalysis” Lowell, MA 01852 email: srodman(at)konarka.com N Prof. Phil Dawson (Scripps Research Institute) Boston College, Merkert 130 “Synthetic Protein Engineering” 4:00 pm Boston College, Merkert 130 Feb 18 4:00 pm Helmut Schwarz (Technical University of Your one-stop source to career-related Feb 03 Berlin) links in the Chemical Sciences Thomas Rauchfuss (Univ. Illinois at Urbana Harvard, Pfizer Lecture Hall Champaign) 4:00 pm WWW.NESACS.ORG/CAREERS MIT, 6-120 4:15 pm