enantioselective desymmetrization of cyclobutanones ...ccc.chem.pitt.edu/wipf/current...

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1 Wang, M.; Chen, J.; Chen, Z.; Zhong, C.; Lu, P. Angew. Chem. Int. Ed. 2018, 57, 2707-2711 Leila Terrab Wipf Group Current Litterature 04/14/2018 Enantioselective Desymmetrization of Cyclobutanones Enabled by Synergistic Palladium/Enamine Catalysis Leila Terrab @ Wipf Group Page 1 of 13 6/23/2018

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Page 1: Enantioselective Desymmetrization of Cyclobutanones ...ccc.chem.pitt.edu/wipf/Current Literature/Leila_5.pdfChem. Rev. 116, 12, 7330-7396 3 Rh-catalyzed Intramolecular alkene insertion

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Wang, M.; Chen, J.; Chen, Z.; Zhong, C.; Lu, P.Angew. Chem. Int. Ed. 2018, 57, 2707-2711

Leila TerrabWipf Group

Current Litterature04/14/2018

Enantioselective Desymmetrization of Cyclobutanones Enabled by

Synergistic Palladium/Enamine Catalysis

Leila Terrab @ Wipf Group Page 1 of 13 6/23/2018

Page 2: Enantioselective Desymmetrization of Cyclobutanones ...ccc.chem.pitt.edu/wipf/Current Literature/Leila_5.pdfChem. Rev. 116, 12, 7330-7396 3 Rh-catalyzed Intramolecular alkene insertion

Previous enantiomeric syntheses of cyclobutanes

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J. Am. Chem. Soc. 1992, 114, 8869–8885

J. Am. Chem. Soc. 2007, 129, 8930–8931

J. Am. Chem. Soc. 2017, 139, 9120–9123Leila Terrab @ Wipf Group Page 2 of 13 6/23/2018

Page 3: Enantioselective Desymmetrization of Cyclobutanones ...ccc.chem.pitt.edu/wipf/Current Literature/Leila_5.pdfChem. Rev. 116, 12, 7330-7396 3 Rh-catalyzed Intramolecular alkene insertion

Reactions with cyclobutanones

3Chem. Rev. 116, 12, 7330-7396

Rh-catalyzed Intramolecular alkene insertion of cyclobutanones:

Chiral Phosphoric Acid-catalyzed enantioselective Baeyer-Villiger Oxidation

Leila Terrab @ Wipf Group Page 3 of 13 6/23/2018

Page 4: Enantioselective Desymmetrization of Cyclobutanones ...ccc.chem.pitt.edu/wipf/Current Literature/Leila_5.pdfChem. Rev. 116, 12, 7330-7396 3 Rh-catalyzed Intramolecular alkene insertion

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Stoltz group:

Catalytic enantioselective cyclobutanone alkylation

Angew. Chem. Int. Ed. 2013, 52, 6718-6721Leila Terrab @ Wipf Group Page 4 of 13 6/23/2018

Page 5: Enantioselective Desymmetrization of Cyclobutanones ...ccc.chem.pitt.edu/wipf/Current Literature/Leila_5.pdfChem. Rev. 116, 12, 7330-7396 3 Rh-catalyzed Intramolecular alkene insertion

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α-Arylation via Pd/enamine ‘cooperative’ catalysis

1) Enamine formation2) Heck arylation

J. Am. Chem. Soc. 2016, 138, 5198-5201

Chem. Rev. 2016, 116, 13512−13570J. Am. Chem. Soc. 2016, 138, 5198-5201

This paper:

Leila Terrab @ Wipf Group Page 5 of 13 6/23/2018

Page 6: Enantioselective Desymmetrization of Cyclobutanones ...ccc.chem.pitt.edu/wipf/Current Literature/Leila_5.pdfChem. Rev. 116, 12, 7330-7396 3 Rh-catalyzed Intramolecular alkene insertion

Previous α-arylation of cyclobutanones

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Britton group:

Angew. Chem. Int. Ed. 2017, 56, 748-752.Leila Terrab @ Wipf Group Page 6 of 13 6/23/2018

Page 7: Enantioselective Desymmetrization of Cyclobutanones ...ccc.chem.pitt.edu/wipf/Current Literature/Leila_5.pdfChem. Rev. 116, 12, 7330-7396 3 Rh-catalyzed Intramolecular alkene insertion

O-tethered cyclobutanone reaction optimization

7Leila Terrab @ Wipf Group Page 7 of 13 6/23/2018

Page 8: Enantioselective Desymmetrization of Cyclobutanones ...ccc.chem.pitt.edu/wipf/Current Literature/Leila_5.pdfChem. Rev. 116, 12, 7330-7396 3 Rh-catalyzed Intramolecular alkene insertion

N-tethered cyclobutanone reaction optimization

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Poor conversion observed with chiral amines

Leila Terrab @ Wipf Group Page 8 of 13 6/23/2018

Page 9: Enantioselective Desymmetrization of Cyclobutanones ...ccc.chem.pitt.edu/wipf/Current Literature/Leila_5.pdfChem. Rev. 116, 12, 7330-7396 3 Rh-catalyzed Intramolecular alkene insertion

Scope of O-tether analogs

9Leila Terrab @ Wipf Group Page 9 of 13 6/23/2018

Page 10: Enantioselective Desymmetrization of Cyclobutanones ...ccc.chem.pitt.edu/wipf/Current Literature/Leila_5.pdfChem. Rev. 116, 12, 7330-7396 3 Rh-catalyzed Intramolecular alkene insertion

Scope of N-tether analogs

10Leila Terrab @ Wipf Group Page 10 of 13 6/23/2018

Page 11: Enantioselective Desymmetrization of Cyclobutanones ...ccc.chem.pitt.edu/wipf/Current Literature/Leila_5.pdfChem. Rev. 116, 12, 7330-7396 3 Rh-catalyzed Intramolecular alkene insertion

Carbon chain instead of heteroatom tether

11Leila Terrab @ Wipf Group Page 11 of 13 6/23/2018

Page 12: Enantioselective Desymmetrization of Cyclobutanones ...ccc.chem.pitt.edu/wipf/Current Literature/Leila_5.pdfChem. Rev. 116, 12, 7330-7396 3 Rh-catalyzed Intramolecular alkene insertion

Further Transformations of Cyclobutanones

12Leila Terrab @ Wipf Group Page 12 of 13 6/23/2018

Page 13: Enantioselective Desymmetrization of Cyclobutanones ...ccc.chem.pitt.edu/wipf/Current Literature/Leila_5.pdfChem. Rev. 116, 12, 7330-7396 3 Rh-catalyzed Intramolecular alkene insertion

Conclusion

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Use of cooperative Pd/amine catalysis in the intramolecular α- arylation of cyclobutanones

α- Arylation approach similar to the Britton group: used cyclohexanones

Leila Terrab @ Wipf Group Page 13 of 13 6/23/2018