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Figure 1. The roquefortine family of fungal metabolites. Copyright © 2008 American Chemical Society ASAP J. Am. Chem. Soc., ASAP Article, 10.1021/ja800067q;

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Presentation on theme: "Figure 1. The roquefortine family of fungal metabolites. Copyright © 2008 American Chemical Society ASAP J. Am. Chem. Soc., ASAP Article, 10.1021/ja800067q;"— Presentation transcript:

1 Figure 1. The roquefortine family of fungal metabolites. Copyright © 2008 American Chemical Society ASAP J. Am. Chem. Soc., ASAP Article, 10.1021/ja800067q; Web Release Date: April 16, 2008 The Total Synthesis of Roquefortine C and a Rationale for the Thermodynamic Stability of Isoroquefortine C over Roquefortine C Ning Shangguan, Warren J. Hehre, William S. Ohlinger, Mary Pat Beavers, and Madeleine M. Joullié *

2 Figure 2. Isoroquefortine C (4). Copyright © 2008 American Chemical Society ASAP J. Am. Chem. Soc., ASAP Article, 10.1021/ja800067q; Web Release Date: April 16, 2008 The Total Synthesis of Roquefortine C and a Rationale for the Thermodynamic Stability of Isoroquefortine C over Roquefortine C Ning Shangguan, Warren J. Hehre, William S. Ohlinger, Mary Pat Beavers, and Madeleine M. Joullié *

3 Figure 3. Retrosynthetic analysis of roquefortine C (2). Copyright © 2008 American Chemical Society ASAP J. Am. Chem. Soc., ASAP Article, 10.1021/ja800067q; Web Release Date: April 16, 2008 The Total Synthesis of Roquefortine C and a Rationale for the Thermodynamic Stability of Isoroquefortine C over Roquefortine C Ning Shangguan, Warren J. Hehre, William S. Ohlinger, Mary Pat Beavers, and Madeleine M. Joullié *

4 Scheme 1. Construction of the Pyrroloindole Segment (5) Copyright © 2008 American Chemical Society ASAP J. Am. Chem. Soc., ASAP Article, 10.1021/ja800067q; Web Release Date: April 16, 2008 The Total Synthesis of Roquefortine C and a Rationale for the Thermodynamic Stability of Isoroquefortine C over Roquefortine C Ning Shangguan, Warren J. Hehre, William S. Ohlinger, Mary Pat Beavers, and Madeleine M. Joullié *

5 Scheme 2. Synthesis of the Imidazole Derivative (7) Copyright © 2008 American Chemical Society ASAP J. Am. Chem. Soc., ASAP Article, 10.1021/ja800067q; Web Release Date: April 16, 2008 The Total Synthesis of Roquefortine C and a Rationale for the Thermodynamic Stability of Isoroquefortine C over Roquefortine C Ning Shangguan, Warren J. Hehre, William S. Ohlinger, Mary Pat Beavers, and Madeleine M. Joullié *

6 Scheme 3. Route to Isoroquefortine C (4) Copyright © 2008 American Chemical Society ASAP J. Am. Chem. Soc., ASAP Article, 10.1021/ja800067q; Web Release Date: April 16, 2008 The Total Synthesis of Roquefortine C and a Rationale for the Thermodynamic Stability of Isoroquefortine C over Roquefortine C Ning Shangguan, Warren J. Hehre, William S. Ohlinger, Mary Pat Beavers, and Madeleine M. Joullié *

7 Scheme 4. Completion of the Synthesis of Roquefortine C (2) Copyright © 2008 American Chemical Society ASAP J. Am. Chem. Soc., ASAP Article, 10.1021/ja800067q; Web Release Date: April 16, 2008 The Total Synthesis of Roquefortine C and a Rationale for the Thermodynamic Stability of Isoroquefortine C over Roquefortine C Ning Shangguan, Warren J. Hehre, William S. Ohlinger, Mary Pat Beavers, and Madeleine M. Joullié *

8 Figure 4. Isoroquefortine C 4 and two tautomers of roquefortine C (2a and 2b) were the low energy tautomers selected for Hartree–Fock/6-31G* calculations in Spartan 06. Copyright © 2008 American Chemical Society ASAP J. Am. Chem. Soc., ASAP Article, 10.1021/ja800067q; Web Release Date: April 16, 2008 The Total Synthesis of Roquefortine C and a Rationale for the Thermodynamic Stability of Isoroquefortine C over Roquefortine C Ning Shangguan, Warren J. Hehre, William S. Ohlinger, Mary Pat Beavers, and Madeleine M. Joullié *

9 Figure 5. 3-Dimensional structural representations of isoroquefortine C, tautomer 1 of roquefortine C, and tautomer 2 of roquefortine C based on HF/6-31G* geometry optimizations. Both isoroquefortine C (4) and tautomer (2) of roquefortine C (2b) have intramolecular H-bonds between the imidazole and diketopiperazine rings. The atoms circled in red denote the centers (sp 2, nitrogen, carbon, and hydrogen atoms) involved in the “rings” representing the coplanar double bond networks. Copyright © 2008 American Chemical Society ASAP J. Am. Chem. Soc., ASAP Article, 10.1021/ja800067q; Web Release Date: April 16, 2008 The Total Synthesis of Roquefortine C and a Rationale for the Thermodynamic Stability of Isoroquefortine C over Roquefortine C Ning Shangguan, Warren J. Hehre, William S. Ohlinger, Mary Pat Beavers, and Madeleine M. Joullié *

10 Figure 6. Vinyl imidazole. The barrier to rotation of the exocyclic double bond out of coplanarity was modeled using HF/6-31G*. If the double bond rotates out of coplanarity with the conjugated imidazole ring, the penalty is in the range of 17–23 kJ/mol, depending on the starting tautomer and conformer. Copyright © 2008 American Chemical Society ASAP J. Am. Chem. Soc., ASAP Article, 10.1021/ja800067q; Web Release Date: April 16, 2008 The Total Synthesis of Roquefortine C and a Rationale for the Thermodynamic Stability of Isoroquefortine C over Roquefortine C Ning Shangguan, Warren J. Hehre, William S. Ohlinger, Mary Pat Beavers, and Madeleine M. Joullié *

11 Figure 7. Cyclopentadiene analogues of isoroquefortine C and roquefortine C (25 and 26, respectively). The isoroquefortine C analogue (25) is 14 kJ/mol more stable than the roquefortine C analogue (26) from HF/6-31G* and 9 kJ/mol from T1. Copyright © 2008 American Chemical Society ASAP J. Am. Chem. Soc., ASAP Article, 10.1021/ja800067q; Web Release Date: April 16, 2008 The Total Synthesis of Roquefortine C and a Rationale for the Thermodynamic Stability of Isoroquefortine C over Roquefortine C Ning Shangguan, Warren J. Hehre, William S. Ohlinger, Mary Pat Beavers, and Madeleine M. Joullié *

12 Figure 8. 3-Dimensional structural representations of cyclopentadienyl analogues of isoroquefortine C and roquefortine C (25 and 26) based on HF/6-31G* geometry optimizations. The conjugated double bonds in 25 are nearly coplanar while those in 26 have bond angles that deviate from ideal sp 2 geometries. These double bond networks (in both 25 and 26) involve the exocyclic double bond and the double bond of the Cp ring that it is conjugated to. Copyright © 2008 American Chemical Society ASAP J. Am. Chem. Soc., ASAP Article, 10.1021/ja800067q; Web Release Date: April 16, 2008 The Total Synthesis of Roquefortine C and a Rationale for the Thermodynamic Stability of Isoroquefortine C over Roquefortine C Ning Shangguan, Warren J. Hehre, William S. Ohlinger, Mary Pat Beavers, and Madeleine M. Joullié *

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