![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](https://reader031.vdocuments.mx/reader031/viewer/2022011913/5fb16fe2ea9ab71d945f3400/html5/thumbnails/1.jpg)
1
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](https://reader031.vdocuments.mx/reader031/viewer/2022011913/5fb16fe2ea9ab71d945f3400/html5/thumbnails/2.jpg)
Previous enantiomeric syntheses of cyclobutanes
2
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](https://reader031.vdocuments.mx/reader031/viewer/2022011913/5fb16fe2ea9ab71d945f3400/html5/thumbnails/3.jpg)
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](https://reader031.vdocuments.mx/reader031/viewer/2022011913/5fb16fe2ea9ab71d945f3400/html5/thumbnails/4.jpg)
4
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](https://reader031.vdocuments.mx/reader031/viewer/2022011913/5fb16fe2ea9ab71d945f3400/html5/thumbnails/5.jpg)
5
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](https://reader031.vdocuments.mx/reader031/viewer/2022011913/5fb16fe2ea9ab71d945f3400/html5/thumbnails/6.jpg)
Previous α-arylation of cyclobutanones
6
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](https://reader031.vdocuments.mx/reader031/viewer/2022011913/5fb16fe2ea9ab71d945f3400/html5/thumbnails/7.jpg)
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](https://reader031.vdocuments.mx/reader031/viewer/2022011913/5fb16fe2ea9ab71d945f3400/html5/thumbnails/8.jpg)
N-tethered cyclobutanone reaction optimization
8
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](https://reader031.vdocuments.mx/reader031/viewer/2022011913/5fb16fe2ea9ab71d945f3400/html5/thumbnails/9.jpg)
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](https://reader031.vdocuments.mx/reader031/viewer/2022011913/5fb16fe2ea9ab71d945f3400/html5/thumbnails/10.jpg)
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](https://reader031.vdocuments.mx/reader031/viewer/2022011913/5fb16fe2ea9ab71d945f3400/html5/thumbnails/11.jpg)
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](https://reader031.vdocuments.mx/reader031/viewer/2022011913/5fb16fe2ea9ab71d945f3400/html5/thumbnails/12.jpg)
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](https://reader031.vdocuments.mx/reader031/viewer/2022011913/5fb16fe2ea9ab71d945f3400/html5/thumbnails/13.jpg)
Conclusion
13
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