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2.2.4.1.5 Photoinduced Coupling Reactions

DOI: 10.1055/sos-SD-213-00070

Ballini, R.; Petrini, M.Science of Synthesis: C-1 Building Blocks in Organic Synthesis, (20142139.

Photoredox catalysis is based on the property of certain organic and organometallic compounds to display a higher redox character in the excited state compared to the parent ground state.[‌18‌] In these compounds, excitation can be obtained by irradiation with visible light usually provided by a household fluorescent lamp. Organometallic complexes of iridium(III) and ruthenium(II) with bipyridine derivatives are the most active compounds in which the excited state originates from a metal-to-ligand charge-transfer process. As a result, the redox potential can be suitably tuned by the correct choice of metal ligand in these complexes. The general mechanism involves excitation of the catalyst by visible light, followed by oxidation of the tertiary amine by a single-electron-transfer process (Scheme 9).[‌19‌] This generates a radical cation, while the reduced catalyst is re-oxidized by an external oxidant or by the nitromethane, giving a radical anion. Reaction between the two charged radical species affords the iminium ion, which finally adds to the anion of nitromethane, leading to the final product.

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MMe MMe Me 88 88 [‌88‌]
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M M 8-Mee eeeee M (8) 88 88 88 [‌88‌]
MMe MMe Me eeee Meeeee (8) 888 8 88 [‌88‌]

Meeeeeeeeeee Meeeeeeee

8-Meee-8-(eeeeeeeeeee)-8,8,8,8-eeeeeeeeeeeeeeeeeeeeeee 88; Meeeeee Meeeeeeee:[‌88‌]

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8-Meee-8-(eeeeeeeeeee)-8,8,8,8-eeeeeeeeeeeeeeeeeeeeeee 88; Meeeeee Meeeeeeee Meeee Meeee M:[‌88‌]

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References


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