Craig Ogle, Professor

Craig Ogle, Professor Post-doctoral Associate University of Lausanne, Lausanne Switzerland Ph.D. University of Arizona MS University of Arizona BA Otterbein College
Publications

My research has centered on the preparation, reaction and structure of carbanionic species. We are currently preparing organometallic reagents as chiral auxiliaries for organic synthesis. We are preparing functional monomers for preparing functional polymers. We are using the rapid injection NMR technique to help understand the mechanisms for organometallic conjugate addition reactions. A list of recent publications from my research group can be viewed at below.

Chemistry, A European Journal, 1999, 2680 (1999).

Re-evaluation of Organocuprate Reactivity. Logarithmic Reactivity Profiles for Iodo- vs. Cyano-Gilman Reagents in the Reactions of Organocuprates with 2-Cyclohexenone and Iodocyclohexane.**

Steven H. Bertz,* Anu Chopra, Magnus Eriksson, Craig A. Ogle,* and Paul Seagle

Dedicated to Professor Martin Nilsson on the occasion of his 70th birthday.

ABSTRACT

Iodo-Gilman reagents Me₂CuLi·LiI, Bu₂CuLi·LiI, and BuThCuLi·LiI and cyano-Gilman reagents (formerly called "higher order cyanocuprates") Me₂CuLi·LiCN, Bu₂CuLi·LiCN, and BuThCuLi·LiCN react with 2-cyclohexenone at various rates, which depend upon the solvent, Li salt (i.e., Cu(I) precursor) and amount of chlorotrimethylsilane (TMSCl) additive. The effect of Li salt is less than that of solvent or TMSCl, which contradicts the myth of extraordinary reactivity for the cyanocuprates. The cuprate-iodocyclohexane reaction has also been examined as a function of Li salt, solvent and TMSCl additive, and similar effects are observed. The effect of solvent is more dramatic and the effect of TMSCl is less pronounced; nevertheless, this is the first demonstration of a TMSCl-effect with a substrate that does not contain an oxygen that is silylated. The reactivity matrix R with elements R_i,j is a convenient way to store and present a large amount of relative reactivity data. R_i,j is the ratio of the yield with reagent i to the yield with reagent j. The logarithmic reactivity profile (LRP) provides an effective means for determining yields under conditions where such comparisons are valid. The results of 46 4-point LRPs and related reactions (>200 total) are tabulated and analyzed to provide the first quantitative picture of organocuprate reactivity, which has synthetic and mechanistic implications.

Journal of Polymer Science, Part A Polymer Chemistry, 37, 1157 (1999).

A Rapid-Injection NMR Study of the Effect of Lithium Alkoxides on the Butyllithium Initiated Polymerization and Propagation of Styrene

Craig A. Ogle*^o , Xiao Li Wang^o , Clifford M. Carlin^o, Frederick H. Strickler^# and Bernard Gordon III*^#
^oDepartment of Chemistry, University of North Carolina at Charlotte, Charlotte, NC 28223 and
^#Department of Materials Science and Engineering, Polymer Science Program
Pennsylvania State University, University Park, PA 16802

Abstract: In studies carried out in THF at –80 ° C, lithium n-butoxide was found to speed up the initiation and to an even a greater extent the rate of propagation in the alkyllithium initiated polymerization of styrene. Bulky alkoxides were found to slow down the rate of polymerization by slowing both initiation and propagation although initiation was decreased to a greater extent than propagation. Five equivalents of lithium tert-butoxide stopped the initiation completely under these reaction conditions when n-butyllithium was used as an initiator.

Published in Main Group Metal Chemistry, 21, 777 (1998).

Benzyllithium: Preparation, Reactions and X-ray Crystal Structure of Benzyllithium· 2THF

Marcon Hage,¹ Craig A. Ogle,*¹ Terry L. Rathman² and John L. Hubbard*³

^{1 Department
of Chemistry, University of North Carolina at Charlotte, Charlotte, NC
28223}
^{2 Lithium Division, FMC Corporation,
P.O.Box 795, Bessemer City, NC 28016}

^{3 Department of Chemistry and Biochemistry,
Utah State University, Logan UT 84322}

Abstract: Benzyllithium can be prepared in relatively high concentrations in mixtures of cyclic ethers by metalation of toluene with n- or sec-butyllithium. The solubility and stability goes increases markedly, in mixtures of cyclic ethers, over THF alone. In THF/ toluene, benzyllithium crystallizes out as a linear polymer with alternating C’s and Li’s making up the polymer backbone with each lithium solvated by 2 THF’s.

Main Group Metal Chemistry, 21, 25 (1998).

DIRECTED DILITHIATION OF DIARYL COMPOUNDS:
PREPARATION OF TRICYCLIC PHARMACEUTICALS BASED
ON THE DIBENZOHETEROAZEPINE SKELETON¹

Anu Chopra, Donna C. Dorton and Craig A. Ogle*

Department of Chemistry, University of North Carolina at Charlotte, Charlotte, NC 28223

Abstract: A facile synthesis of pharmacologically important dibenzo[b,f][1,4]heteroazepine based tricyclic compounds is reported. Reaction of diaryl compounds such as o-amino-diphenyl ether and o-amino-diphenyl sulfone with n-butyllithium yielded the C,N-dilithio-diaryl species in excellent yields. These dilithio intermediates were reacted with appropriate ester moieties to synthesize tricyclic compounds based on the dibenzo[b,f][1,4]heteroazepine framework.

7a, X = O	9a, R = 4-pyridyl	10a, 89%	11a, 70%
7a, X = O	9b, R = -(CH₂)₃-NMe₂	10b, 82%
7b, X = SO₂	9c, R = cyclopropyl	10c, 81%

J. Am. Chem. Soc., 124 (46), 13650 - 13651, 2002. 10.1021
Web Release Date: October 29, 2002

Copyright © 2002 American Chemical Society

Rapid-Injection NMR Study of Iodo- and Cyano-Gilman Reagents with 2-Cyclohexenone: Observation of -Complexes and Their Rates of Formation¹

Steven H. Bertz*, Clifford M. Carlin, Daniel A. Deadwyler, Michael D. Murphy*, Craig A. Ogle*, and Paul H. Seagle

Department of Chemistry, University of North Carolina-Charlotte, UNCC Station, Charlotte, North Carolina 28223 and Complexity Study Center, Mendham, New Jersey 07945

Received July 17, 2002

Abstract:

Rapid-injection is a very useful technique for the preparation of temperature-sensitive and air-sensitive compounds in the cold, nitrogen-filled probe of an NMR spectrometer. We have used this method to prepare solutions of -complexes from 2-cyclohexenone and prototypical cuprates Me₂CuLi·LiI and Me₂CuLi·LiCN, and we have assigned structures on the basis of ¹H and ¹³C NMR. In each case two -complexes were observed, and in the former, their rates of formation were measured by rapid-injection ¹H NMR and EXSY spectroscopy. These results provide insights into the normal and anomalous conjugate addition reactions of organocuprates.

Publications:

"Rapid-Injection NMR Study of Iodo- and Cyano-Gilman Reagents with Cyclo-hexenone: Observation of -Complexes and their rate of formation." S. H. Bertz, C. M. Carlin, D. A. Deadwyler, M. D. Murphy, C. A. Ogle, and P. H. Seagle, J. Am. Chem. Soc., 124, 13650-13651(2002).

Chloro(1,5-cyclooctadiene)(triphenylphosphine)-rhodium(I) Q. L. Horn, D. S. Jones,*R. N. Evans, C. A. Ogle and T. Craig Masterman, Acta Crystallographica Section E58, m51-52 (2002).

"Process to selectively place functional groups within polymer chain," United States Patent No. 6,225,415 issued May 1, 2001 to Craig Ogle, assigned to the University of North Carolina at Charlotte.

"Preparation of the Tomato Pinworm Pheromone, (E)-4-Tridecenyl Acetate, from Dihydropyran and n-Octyllithium." Joseph P. Mitchener Jr., J. C. Thomas and C. A. Ogle, Main Group Metal Chemistry, 22, 435 (1999).

"Re-evaluation of Organocuprate Reactivity. Logarithmic Reactivity Profiles for Iodo- vs. Cyano-Gilman Reagents in the Reactions of Organocuprates with 2-Cyclohexenone and Iodocyclohexane." S. H. Bertz, A. Chopra, M. Eriksson, C. A. Ogle, Chemistry, A European Journal. 1999, 2680-92 (1999).

"Lithium Alkoxide Modifiers: Their Effect on the Rate of Polymerization and Propagation of Styrene by Butyllithium, in THF at -80°C." C. A. Ogle, Harry C. Johnson IV, X. L. Wang, C. M. Carlin, F. H. Strickler and B. Gordon III, J. Poly. Science Part. A Polymer Chemistry, 37, 1157-68 (1999).

"Benzyllithium: Preparation, Reactions and X-RAY Crystal Structure of Benzyllithium"2THF" M. Hage, C. A. Ogle, T. L. Rathman and J. L. Hubbard, Main Group Met. Chem. 21, 777 (1998).

"Directed Dilithiation of Diaryl Compounds: Preparation of Tricyclic Pharmaceuticals Based on the Dibenzoheteroazapine Skeleton." A. Chopra, D. C. Dorton and C. A. Ogle, Main Group Met. Chem., 21, 25 (1998).

"Directed Ortho Dilithiation of Diaryl Compounds: Facile Synthesis of Tricyclic Compounds Based on Heterocycles Fused to Two Benzene Rings." A. Chopra, D. C. Dorton and C. A. Ogle, Main Group Met. Chem., 20, 783 (1997).

"A Novel Approach to Tricyclic Pharmaceuticals via Directed Dilithiation of Diaryl Compounds." V. B. Birman, A. Chopra and C. A. Ogle, Tetrahedron Letters, 37, 5073 (1996).