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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.
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.
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
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.
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.
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,
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,
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.
For a complete list of publications,
go to Merlic Page 2.
Merlic Research Group Page
University of California, Los Angeles
Department of Chemistry and Biochemistry
607 Charles E. Young Drive East
Los Angeles, CA 90095-1569
Updated on 6/22/00 by Alice Ramirez: firstname.lastname@example.org