Craig A. Merlic

B.S. 1982, University of California, Davis; Ph.D. 1988, University of Wisconsin, Madison; NIH Postdoctoral Fellow 1988-1989, Princeton University; National Science Foundation Young Investigator Award, 1992-1997; Camille Dreyfus Teacher-Scholar Award, 1994-1999; Alfred P. Sloan Research Fellowship, 1995-1997.

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RESEARCH INTERESTS

Merlic Group Web Page

Our research program in organic and organometallic chemistry encompasses synthetic organic, synthetic organometallic, and physical organometallic chemistry. Research goals include discovery of new reactions and catalysts, development of synthetic methods, new techniques for asymmetric synthesis, determination of reaction mechanisms, synthesis of bioactive natural products and development of organometallic complexes for materials research. The development of new chemistry using organometallic species is a rich and fertile area due to the unique ability of transition metal fragments to impart special reactivity, selectivity, and stability upon bonded organic moieties. Our research draws on these features to address problems in organic synthesis.

Organometallic Radical Reactions for Stereoselective Synthesis

Organometallic radical reactions are being investigated as new methods for carbon-carbon bond formation. By using transition metal fragments totemplate the reactions of organic moieties, control of chemoselectivity, regiochemistry and stereochemistry in radical cyclizations is feasible. A wide array of organometallic compounds are employed including iron olefin complexes, cobalt alkyne complexes, iron triene complexes, chromium carbene complexes and arene chromium complexes. The later are used for asymmetric synthesis where both enantiomers of a product are available from a single starting enantiomer. Applications of the newly developed methods to the syntheses of biologically active products such as antitumor agents, unnatural sugars, and antibiotics are under investigation.

Synthesis Via Metal-Mediated Pericyclic Reactions and Fischer Carbene Complexes

We are exploring fundamentally new types of pericyclic reactions by incorporating metal fragments into reacting polyene arrays. The metals can participate directly in pericyclic reactions or can serve as templates to control reaction selectivity. Examples include a variety of annulations employing chromium carbene complexes, while second generation reactions will employ metal fragments catalytically. Topics we seek to address in organometallic pericyclic reactions include reaction mechanisms, selectivity rules, substrate variability and synthetic applications. These new methods are being applied in the synthesis of a number of structurally diverse antibiotic, antiimflammatory and antitumor agents.

Asymmetric Synthesis and Catalysis

While stoichiometric implementation of transition metal organometallic chemistry provides for unique molecular transformations, the real power of transition metal complexes lies in catalysis. Single catalytic reactions can replace multiple steps in traditional organic synthesis and do so with lower costs in an environmentally friendly manner. Catalysts are under investigation for precesses including asymmetric synthesis, carbon-heteroatom bond formation, multicomponent coupling, cycloisomerizations and pericyclic reactions. Most of these focus on the use of homogeneous palladium and ruthenium catalysis. New methods of catalyst immobilization that facilitate recycling and reuse are also being explored.

Merlic Group Web Page

RECENT PUBLICATIONS

1. Merlic, C.A.; Xu, D. "Cyclization Reactions of Dienyl Chromium Carbene Complexes. Entry to Ortho Substituted Aromatic Alcohols via a Designed Photoreaction" J. Am. Chem. Soc. 1991, 113, 7418-7420.

2. Merlic, C.A.; Xu, D. "Intermolecular Radical Reactions of Unsaturated Chromium and Tungsten Carbene Complexes," J. Am. Chem. Soc. 1991, 113, 9855-9856.

3. Merlic, C. A.; Xu, D.; Khan, S. I. "Synthesis, Structure and Reactivity of Cyclic Arene Chromium Carbene Complexes" Organometallics 1992, 11, 412-418.

4. Merlic, C. A.; Burns, E. E.; Xu, D.; Chen, S. Y. "Aminobenzannulation Via Metathesis of Isonitriles Using Chromium Carbene Complexes" J. Am. Chem. Soc. 1992, 114, 8722-8724.

5. Merlic, C. A.; Xu, D; Gladstone, B. "Aminobenzannulation Via Photocyclization Reactions of Chromium Dienyl(Amino)carbene Complexes. Synthesis of Ortho Amino Aromatic Alcohols" J. Org. Chem. 1993, 58, 538-545.

6. Merlic, C. A.; Bendorf, H. D. "Titanium-Templated [4+2] Oxidative Cycloadditions: A Facile Route to 7-Hydroxynorbornenes" Organometallics 1993, 12, 559-564.

7. Merlic, C. A.; Burns, E. E. "Chemoselectivity in the Isonitrile Metathesis Route to Aromatic Amines" Tetrahedron Lett. 1993, 34, 5401-5404.

8. Merlic, C. A.; Bendorf, H. D. "Cyclopropanation of C60 Via a Fischer Carbene Complex" Tetrahedron Lett. 1994, 35, 9529-9532.

9. Merlic, C. A.; Albaneze, J. "Rapid Synthesis of Functionalized, Alkoxy-Substituted, Allylstannanes from Carbene Complexes" Tetrahedron Lett. 1995, 36, 1007-1010.

10. Merlic, C. A.; Albaneze, J. "Synthesis of Alkoxy-Substituted Allenyl- and Propargylstannane Reagents from Carbene Complexes" Tetrahedron Lett. 1995, 36, 1011-1014.

11. Merlic, C. A.; Motamed, S.; Quinn, B. "Structure Determination and Synthesis of Fluoro Nissl Green: An RNA Binding Fluorochrome" J. Org. Chem. 1995, 60, 3365-3369.

12. Merlic, C. A.; Pauly, M. E. "Ruthenium-Catalyzed Cyclizations of Dienylalkynes Via Vinylidene Intermediates" J. Am. Chem. Soc. 1996, 118, 11319-11320.

13. Merlic, C. A.; McInnes, D. M.; You, Y. "Synthesis of Indolocarbazoles via Annulations of Chromium Carbene Complexes" Tetrahedron Lett. 1997, 38, 6787-6790.

14. Merlic, C. A.; McInnes, D. M. "Synthesis of Indolocarbazoles via Sequential Palladium Catalyzed Cross Coupling and Benzannulation Reactions" Tetrahedron Lett. 1997, 38, 7661-7664.

15. Merlic, C. A.; Wu, F. "Synthesis of b-Keto Fischer Carbene Complexes" Journal of Organometallic Chemistry 1998, 553, 183-191.

16. Merlic, C. A.; Walsh, J. C. "Completely Diastereoselective Radical Reactions Using Arenechromium Tricarbonyl Complexes" Tetrahedron Lett. 1998, 39, 2083-2086.

17. Merlic, C. A.; Walsh, J. C.; Tantillo, D. J.; Houk, K. N. "Chemical Hermaphroditism: The Potential of the Cr(CO)3 Moiety to Stabilize Transition States and Intermediates with Anion Cationic, Radical Character at the Benzylic Position" J. Am. Chem. Soc. 1999, 121, 3596-3606.

18. Merlic, C. A.; Aldrich, C. C.; Albaneze-Walker, J.; Saghatelian, A. "Carbene Complexes in the Synthesis of Complex Natural Products: Total Synthesis of the Calphostins" J. Am. Chem. Soc., 2000, 122, 3224-3225.

19. Merlic, C. A.; Baur, A.; Yamada, K.; Brown, S. E. "Synthesis of Quadruply Carbon-13 Labeled Tetramethyltetrathiafulvalene " Syn. Commun. 2000, 30, 2677-2685.

20. Tantillo, D. J.; Hietbrink, B. N.; Merlic, C. A.; Houk, K. N. "Attenuating and Supplanting Nonclassical Stabilization: Cr(CO)3-Complexed Benzonorbornenyl Cations" J. Am. Chem. Soc. 2000, 122, 7136-7137.

21. Merlic, C. A.; Baur, A.; Aldrich, C. C. "Acylamino Chromium Carbene Complexes: Direct Carbonyl Insertion, Formation of Münchnones and Trapping with Dipolarophiles" J. Am. Chem. Soc.. 2000, 122, 7398-7399.

22. Chow, D. S.; Zamborszky, F.; Alavi, B.; Tantillo, D. J.; Baur, A.; Merlic, C. A.; Brown, S. E. "Charge Ordering in the TMTTF Family of Molecular Conductors" Phys. Rev. Lett. 2000, 85, 1698-1701.

23. Merlic, C. A.; Fam, B. C.; Miller, M. M. "WebSpectra: Online NMR and IR Spectra for Students" J. Chem. Ed. 2001, 78, 118-120.

24. Merlic, C. A.; Miller, M. "Neighboring Group Participation by Chromium in Substitution Reactions of (h6-Arene)tricarbonylchromium Complexes" Organometallics 2001, 20, 373-375.

25. Merlic, C. A.; Aldrich, C. C. Albaneze-Walker, J.; Saghatelian, A.; Mammen, J. "Total Synthesis of the Calphostins: Application of Fischer Carbene Complexes and Thermodynamic Control of Atropisomers" J. Org. Chem. 2001, 66, 297-1309..

26. Merlic, C. A.; Miller, M.; Hietbrink, B. N.; Houk, K. N. "Reactivity of (h6-Arene)tricarbonylchromium Complexes Toward Additions of Anions, Cations, and Radicals" J. Am. Chem. Soc. 2001, 123, 4904-4918.

27. Merlic, C. A.; McInnes, D. M.; You, Y.; Zechman, A. L.; Miller, M. M.; Deng, Q." Benzannulation Reactions of Fischer Carbene Complexes for the Synthesis of Indolocarbazoles " Tetrahedron 2001, 57, 5199-5212.

28. Merlic, C. A.; Walsh, J. "The Tricarbonylchromium Template for Stereocontrol in Radical Reactions of Arenes " J. Org. Chem. 2001, 66, 2265-2274.

For a complete list of publications, go to Merlic Page 2.

ADDITIONAL INFORMATION

The Merlic Research Group Page

Email: merlic@chem.ucla.edu
Phone: 310-825-5466

Fax: 310-206-3722

University of California, Los Angeles
Department of Chemistry and Biochemistry
607 Charles E. Young Drive East
Los Angeles, CA 90095-1569

Updated on 2/13/03 by Alice Ramirez: alice@chem.ucla.edu