PHOTOCATALYTIC FLUOROALKYLATION REACTIONS OF ORGANIC COMPOUNDS

BARATA VALLEJO, SEBASTIAN; BONESI S. M.; POSTIGO J. ALBERTO

ORGANIC & BIOMOLECULAR CHEMISTRY

ROYAL SOC CHEMISTRY

Lugar: CAMBRIDGE; Año: 2015 vol. 13 p. 11153 - 11183

1477-0520

INDEXABSTRACTINTRODUCTION1.-TRANSITION METAL PHOTOORGANOCATALYSIS1.1.- TRANSITION METAL-PHOTOCATALYTIC FLUOROALKYLATION OF ALIPHATIC COMPOUNDS1.1.1.-FLUOROALKYLATION OF SP3 CARBON ATOMS1.1.2.-FLUOROALKYLATION OF SP2 and SP CARBON ATOMS1.2.-TRANSITION METAL-PHOTOCATALYTIC FLUOROALKYLATION OF (HETERO)ARENES1.2.1.-ARENES1.2.2.-HETEROARENES2.-PHOTOORGANOCATALYSIS (POC)2.1.-FLUOROALKYLATION OF ALIPHATIC SYSTEMS BY POC2.1.1.-FLUOROALKYLATION OF SP3CARBON ATOMS BY POC2.1.2.-FLUOROALKYLATION OF SP2 CARBON ATOMS BY POC2.2.-FLUOROALKYLATION OF AROMATIC SYSTEMS BY POC2.2.1.-ARENES3. MISCELLANEOUS4.-REFERENCESABSTRACTPhotocatalytic methods for fluoroalkyl-radical generation provide more convenient alternatives to the classical perfluoroalkyl-radical (Rf) production through chemical initiators, such as azo or peroxide initiators or the employment of transition metals through thermal electron transfer (ET) reactions. The mild photocatalytic reaction conditions tolerate a variety of functional groups and, thus, are handy to the ulterior modification of bioactive molecules. Transition metal-photocatalytic reactions for Rf radical generation profit from the redox properties of coordinatively saturated Ru or Ir organocomplexes to act as both electron donor and reductive species, thus allowing for the utilization of electron accepting and donating fluoroalkylating agents for Rf radical production. On the other hand, photoorgano catalysts (POC), through the use of proper organic molecules, in the absence of transition metals, can also act as electron exchange species upon excitation, resulting in ET reactions that produce Rf radicals. In this work, a critic account of transition metal, and transition metal-free Rf radical production will be described with photoorgano catalysts, studying classical examples and the most recent investigations in the field.