Aryl Ketone Mediated Light-Driven Naphthylation of C(sp³)–H Bonds Attached to either Oxygen or Nitrogen Substituents

Abstract

A light-driven naphthylation was achieved at C(sp³)–H bonds attached to either oxygen or nitrogen substituents using sulfonylnaphthalenes as a naphthalene precursor in the presence of 4-benzoylpyridine at ambient temperature. The present transformation is proposed to proceed through the generation of a carbon radical species via chemoselective cleavage of the heteroatom-substituted C(sp³)–H bond by photoexcited 4-benzoylpyridine, the addition of the derived carbon radical to the electron-deficient sulfonylnaphthalene, and then rearomatization by releasing sulfinyl radical.

Key words

C–H functionalization - naphthylation - photoreaction - aryl ketones - ethers - amides

Publication History

Received: 11 May 2022

Accepted after revision: 13 June 2022

Accepted Manuscript online:
13 June 2022

Article published online:
02 August 2022

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• 13 A radical chain mechanism, by hydrogen atom abstraction from THF (1a) with in-situ generated methanesulfinyl radical, seems not to be operating in the present case because the reaction ceased when the light was turned off; see Supporting Information for details and also, see: Wang Y.-T, Shih Y.-L, Wu Y.-K, Ryu I. Adv. Synth. Catal. 2022; 364: 1039
• 14 We, indeed, confirmed that the reaction of THF (1a) with 4-methoxy-1-(methylsulfonyl)naphthalene (2j) in the presence of 4-BzPy did not provide the expected product 3aj, and the recovery of a significant amount of the naphthalene precursor 2j was observed.
• 15 The reason for the different reactivities of Ph₂CO, 2-BzPy, 3-BzPy, and 4-BzPy is not clear at the moment.
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• 20 We also measured the kinetic isotope effect (KIE) by treating a mixture of THF (1a) and its fully deuterated analogue 1a-d with the naphthalene precursor 2b under the optimized conditions. The value of the KIE was determined to be 1.6. A relatively small value of the KIE might indicate that the C–H bond cleavage by photoexcited 4-BzPy could be taking place in more concerted fashion, for instance, via electron transfer between photoexcited 4-BzPy and THF followed by proton abstraction. In any case, further investigations are required to clarify the detailed reaction pathway.
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