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. 2023 Oct 6;25(39):7209-7213.
doi: 10.1021/acs.orglett.3c02822. Epub 2023 Sep 26.

Site-Selective Nitration of Aryl Germanes at Room Temperature

Amit Dahiya  1 , Avetik G Gevondian  1 , Aymane Selmani  1 , Franziska Schoenebeck  1
Affiliations

Site-Selective Nitration of Aryl Germanes at Room Temperature

Amit Dahiya et al. Org Lett. .

Abstract

We report a site-selective ipso-nitration of aryl germanes in the presence of boronic esters, silanes, halogens, and additional functionalities. The protocol is characterized by operational simplicity, proceeds at room temperature, and is enabled by [Ru(bpy)3](PF6)2/blue light photocatalysis. Owing to the exquisite robustness of the [Ge] functionality, nitrations of alternative functional handles in the presence of the germane are also feasible, as showcased herein.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
State of art in site-selective C–Ge functionalization, C–H nitration, and ipso-nitration of arenes and this work.
Scheme 1
Scheme 1. Site-Selectivity and Orthogonality of Aryl Germane ipso-Nitration
Without the addition of NaBF4. Reaction time of 7 h. Quantified by 1H NMR against an internal standard. 9% of nitration at silane. Reaction conditions: aryl germane (0.3 mmol, 1.0 equiv), N-nitrosuccinimide (0.6 mmol, 2.0 equiv), [Ru(bpy)3](PF6)2 (0.0075 mmol, 2.5 mol %), NaBF4 (0.45 mmol, 1.5 equiv), and MeCN (1.2 mL). Yields of isolated products are given.
Scheme 2
Scheme 2. DFT Study on Photocatalyzed ipso-Nitration
TS2 could not be located and was approximated as the energy maximum obtained from a relaxed scan of the C-LG bond length. Values (in kcal/mol) refer to Gibbs free energies at the at CPCM (MeCN) M06-2X/def2-TZVP//B3LYP-D3(BJ)/6-31++G(d,p) (LANL2DZ for Ru) level of theory.,
Scheme 3
Scheme 3. Substrate Scope of ipso-Nitration
NaBF4 (0.45 mmol, 1.5 equiv) was used. Reaction conditions: aryl germane (0.3 mmol, 1.0 equiv), N-nitrosuccinimide (0.6 mmol, 2.0 equiv), [Ru(bpy)3](PF6)2 (0.0075 mmol, 2.5 mol %), and MeCN (1.2 mL). Yields of isolated products are given.
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