Stereoinduction in Metallaphotoredox Catalysis

Abstract

Gary Molander completed his undergraduate studies in chemistry at Iowa State University under the tutelageo fP rofessor Richard C. Larock. He earned his PhD at Purdue University with Professor HerbertC. Brown and undertook postdoctoral training with Professor Barry M. Trost at the University of Wisconsin, Madison. He began his academic career at the University of Colorado, Boulder,m oving to the University of Pennsylvaniai n1 999, where he is currently the Hirschmann-Makineni Professor of Chemistry. Scheme 2. Enantioselective photoredox/Ni dual-catalyzed cross-coupling of A) a-trifluoromethyltrifluoroborates and B) a-alkoxymethyltrifluoroborates. Scheme 3. Enantioselective photoredox/Ni dual-catalyzed desymmetrization of A) cyclic meso anhydrides and B) diols. Angewandte Chemie Minireviews Scheme 4. Enantioselective photoredox/Ni dual-catalyzed decarboxylative arylations. Scheme 5. Enantioselective photoredox/Ni dual-catalyzed C(sp 3)-H arylation. Angewandte Chemie Minireviews Scheme 9. Enantioselective photoredox/Ni dual-catalyzed 1,2-carbodifunctionalization of carbamoyl chloride-tethered alkenes. Scheme 10. Mechanism involving photoexcitation of aCu I complex and reductive elimination from Cu III. Scheme 11. Enantioselective C-N cross-couplingoftertiary a-chloroamides with carbazoles and indoles. Scheme 12. Interposing aGiese-type addition prior to formation of the Cu III intermediate enables A) cyanation/fluoroalkylation and B) alkylation/alkynylation or arylation/alkynylationo falkenes. Angewandte Chemie Minireviews Scheme 23. Diastereoselective photoredox/Ni dual-catalyzed 1,2-carbosulfonylationo falkynes.

Asymmetric three-component olefin dicarbofunctionalization enabled by photoredox and copper dual catalysis

“…Given the unique reactivity modes of radical species, the development of radical-mediated alkene vicinal DCF reactions would enable a wider variety of functional groups and synthetic handles to be incorporated, and hence produce valuable target molecules 11 – 15 . While particularly promising, controlling the stereoselectivity in radical alkene vicinal DCF reactions is a long-standing and fundamental challenge due to the intrinsically high reactivity and instability of radical intermediates 16 – 18 . In recent years, owing to their unique single-electron transfer (SET) ability and good coordination with chiral ligands, chiral copper catalysis opened a new and robust platform for the development of asymmetric radical-mediated alkene vicinal DCF reactions (Fig.…”

Three‐Component Alkene Difunctionalization by Direct and Selective Activation of Aliphatic C−H Bonds

“…Recently, radical‐based difunctionalization of alkenes by Ni‐catalyzed reductive cross‐coupling [3] or Ni/photoredox dual catalysis [4] has experienced a great surge of development. Representative work from the groups of Nevado, [3b,g,i, 4g] Molander, [4c,e,h] Chu, [3c] Aggarwal, [4j] Martin, [4i] Koh [3j] etc. has proved the synthetic potential of this method.…”

Asymmetric Three-Component Olefin Dicarbofunctionalization Enabled by Photoredox and Copper Dual Catalysis

“…While particularly promising, controlling the stereoselectivity in radical alkene vicinal dicarbofunctionalization reactions is a long-standing and fundamental challenge due to the intrinsically high reactivity and instability of radical intermediates [16][17][18] . In recent years, owing to their unique singleelectron transfer ability and good coordination with chiral ligands, chiral copper catalysis opened a new and robust platform for development of asymmetric radical-mediated alkene vicinal DCF reactions (Fig.…”