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Topology of Organometallic Radicals How does coordination with transition metals affect reactivity&stereoelectronic parameters of propargyl cation&radical?

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Presentation on theme: "Topology of Organometallic Radicals How does coordination with transition metals affect reactivity&stereoelectronic parameters of propargyl cation&radical?"— Presentation transcript:

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2 Topology of Organometallic Radicals

3 How does coordination with transition metals affect reactivity&stereoelectronic parameters of propargyl cation&radical?

4 Alternative Strategies for Generation of Co2(CO)6 - Complexed Propargyl Radicals

5 Tetrahydrofuran-Mediated Generation and Stereoselective Coupling of Cobalt-Complexed Propargyl Radicals

6 THF: Synthetic Profile

7 Understanding THF-Mediated Radical Reaction: Hydride Ion Transfer versus Direct Single Electron Reduction

8 Mechanism of THF-Mediated Radical Reaction

9 Unorthodox Radical Chemistry

10 Spontaneous Generation of Cobalt- Complexed Propargyl Radicals

11 Tentative Mechanism of Spontaneous Reaction

12 The Effect of Temperature Upon Reaction Rate Gagik G. Melikyan, Boghos Mikailian, Ruth Sepanian, Pogban Toure. High-Temperature Reaction of a Co2(CO)6- Complexed Propargyl Cation. J. Organomet. Chem. 2009, 694,785-794.

13 Yield and d,l-Diastereoselectivity NOT Compromised Temperature TimeYield d,l:meso de 20°C11h80.0%94:688% 40°C100min93.0%94:688% 83°C6min88.0%92:884% 147°C1min84.0%90:1080%

14 High Temperature Reactions in Cobalt- Alkyne Chemistry

15 One-Step, Tf 2 O-Mediated Radical Reaction

16 Generation of Cobalt-Complexed Propargyl Cations under Acidic Conditions

17 Generation of Cobalt-Complexed Propargyl Cations under Acidic Conditions: An Alternative Approach

18 Generation of Cobalt-Complexed Propargyl Cations under Neutral Conditions

19 Expanding Reagent Base: Trifluoroacetic Anhydride vs Triflic Anhydride

20 Expanding Substrate Base of Spontaneous Radical Reaction

21 Can the New Method for Cation Generation Handle Acid- Sensitive Moieties?

22 How Free the Cobalt-Complexed Radicals Are?

23 New Avenue: Cross-Coupling Radical Reactions

24 Charge distribution and structural parameters derived from the PM3 and 3-21G* calculation.

25 Synopsis of Cross-Coupling Radical Reactions

26 Intramolecular Cyclizations: Topology

27 Intramolecular Radical Cyclizations: an Easy Access to 1,5-Cyclodecadiynes

28 Diastereoselectivity of Intramolecular Cyclizations

29 CH/pi-Coordination Leading to meso- Diastereomer

30 X-Ray Structures of 1,5-Alkadiynes & 1,5-Cycloalkadiynes

31 Synthetic Potential

32 Functional Group Tolerance

33 The Concept of Controlling the Concentration of Female Hormones

34 Can Radical Dimers Compete with Testosterone for an Enzymatic Site?

35 Aromatase Inhibitors (AIs): What is on the Market?

36 DNA Cleaving Agents of New Topology

37 Melikyan Research Group Spring 2009

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