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. 2017 Mar 3;7(3):1766-1770.
doi: 10.1021/acscatal.6b03665. Epub 2017 Feb 6.

Mild, Redox-Neutral Alkylation of Imines Enabled by an Organic Photocatalyst

Niki R Patel  1 , Christopher B Kelly  1 , Allison P Siegenfeld  1 , Gary A Molander  1
Affiliations

Mild, Redox-Neutral Alkylation of Imines Enabled by an Organic Photocatalyst

Niki R Patel et al. ACS Catal. .

Abstract

An operationally simple, mild, redox-neutral method for the photoredox alkylation of imines is reported. Utilizing an inexpensive organic photoredox catalyst, alkyl radicals are readily generated from the single-electron oxidation of ammonium alkyl bis(catecholato)silicates and are subsequently engaged in a C-C bond-forming reaction with imines. The process is highly selective, metal-free, and does not require a large excess of the alkylating reagent or the use of acidic additives.

Keywords: hypervalent silicon; imines; photocatalysis; radical alkylation; visible light.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Scheme 1
Scheme 1. Comparison of the Envisioned Photoredox-Mediated Radical Addition to Imines by Alkylsilicate Radical Precursors vs Standard Alkylation Approaches: (a) via Traditional Organometallic Reagents; (b) via Stoichiometric Generation of Radicals; (c) Alternate Photoredox-Based Approach Using Alkylsilicates
Figure 1
Figure 1
Postulated mechanistic pathways for imine alkylation.
Scheme 2
Scheme 2. Successive Photoredox-Catalyzed Alkylation/Cross-Coupling Reactions Alkylsilicates
Scheme 3
Scheme 3. Chemoselectivity in Photoredox Alkylation
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