Metalloalkyl Radical-Mediated Reactions via Metalloradical ... · Metalloalkyl Radical-Mediated...
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Metalloalkyl Radical-Mediated Reactions via Metalloradical Catalysis Prof. X. Peter Zhang’s Research Group Department of Chemistry, Merkert Center, Boston College, Chestnut Hill, MA 02467 Radical Reactions: Opportunities and Challenges The Concept: Metalloradical Catalysis (MRC) L n M• L n M–R 2 C• R 2 C=LG LG R 2 CXY XY Design of Metalloradical Catalysts for MRC L n M• M: Electronic Structure M: Oxidation State L n : Coordination Geometry L n : Size and Dimension SOMO: Orbital Location L n M: Stability Practicality Asymmetric Cyclopropanation: Intramolecular Variant J. Am. Chem. Soc. 2011, 133, 15292. Asymmetric C–H Alkylation with A/A-Substituted Diazos Metalloradical Catalysis (MRC) for Radical Cascade J. Am. Chem. Soc. 2011, 133, 3304; J. Am. Chem. Soc. 2012, 134, 19981. Metalloradical Catalysis for Radical Cyclopropanation J. Am. Chem. Soc. 2010, 132, 10891; J. Am. Chem. Soc. 2011, 133, 8518. Radical Activation via Co(II)-Based Metalloradical Catalysts J. Am. Chem. Soc. 2011, 133, 8518. Metalloradical Catalysis for Radical C–H Alkylation Radical Furanylation Reactions J. Am. Chem. Soc. 2012, 134, 19981. Asymmetric Cyclopropenation of Alkynes J. Am. Chem. Soc. 2011, 133, 3304. Acknowledgments Asymmetric Cyclopropanation: α-Diazoacetates J. Am. Chem. Soc. 2004, 126, 14718; J. Org. Chem. 2007, 72, 5931; J. Am. Chem. Soc. 2007, 129, 12074. Asymmetric Cyclopropanation: α-Ketodiazoacetates Angew. Chem. Int. Ed. 2013, 52, 11857. Asymmetric Cyclopropanation: α-Cyanodiazoacetates J. Am. Chem. Soc. 2010, 132, 12796. A Toolbox of Catalysts: “Group of Six” Chem. Sci. 2015, 6, 1219. R 3 C• R 2 N• RO• NIH: R01-GM098777, R01-GM102554 NSF: CHE-1152767, CHE-1465106 Financial Support
Transcript of Metalloalkyl Radical-Mediated Reactions via Metalloradical ... · Metalloalkyl Radical-Mediated...
Metalloalkyl Radical-Mediated Reactions via Metalloradical CatalysisProf. X. Peter Zhang’s Research Group
Department of Chemistry, Merkert Center, Boston College, Chestnut Hill, MA 02467
Radical Reactions: Opportunities and Challenges The Concept: Metalloradical Catalysis (MRC)
LnM•
LnM–R2C•
R2C=LG
LG
R2CXY
XY
Design of Metalloradical Catalysts for MRC
LnM•
M: Electronic Structure M: Oxidation State
Ln: Coordination Geometry Ln: Size and Dimension
SOMO:
Orbital
Location
LnM:
Stability
Practicality
Asymmetric Cyclopropanation: Intramolecular Variant
J. Am. Chem. Soc. 2011, 133, 15292.
Asymmetric C–H Alkylation with A/A-Substituted Diazos
Metalloradical Catalysis (MRC) for Radical Cascade
J. Am. Chem. Soc. 2011, 133, 3304; J. Am. Chem. Soc. 2012, 134, 19981.
Metalloradical Catalysis for Radical Cyclopropanation
J. Am. Chem. Soc. 2010, 132, 10891; J. Am. Chem. Soc. 2011, 133, 8518.
Radical Activation via Co(II)-Based Metalloradical Catalysts
J. Am. Chem. Soc. 2011, 133, 8518.
Metalloradical Catalysis for Radical C–H Alkylation
Radical Furanylation Reactions
J. Am. Chem. Soc. 2012, 134, 19981.
Asymmetric Cyclopropenation of Alkynes
J. Am. Chem. Soc. 2011, 133, 3304.
Acknowledgments
Asymmetric Cyclopropanation: α-Diazoacetates
J. Am. Chem. Soc. 2004, 126, 14718; J. Org. Chem. 2007, 72, 5931;
J. Am. Chem. Soc. 2007, 129, 12074.
Asymmetric Cyclopropanation: α-Ketodiazoacetates
Angew. Chem. Int. Ed. 2013, 52, 11857.
Asymmetric Cyclopropanation: α-Cyanodiazoacetates
J. Am. Chem. Soc. 2010, 132, 12796.
A Toolbox of Catalysts: “Group of Six”
Chem. Sci. 2015, 6, 1219.
R3C• R2N• RO•
NIH: R01-GM098777, R01-GM102554NSF: CHE-1152767, CHE-1465106
Financial Support
