Photocatalyzed site-selective C(sp3)‒H sulfonylation of toluene derivatives and cycloalkanes with inorganic sulfinates

doi:10.1016/S1872-2067(21)63953-0

Abstract

Abstract:

The development of practical methods for the direct and selective C(sp³)‒H functionalization of hydrocarbons is an attractive topic in synthetic chemistry. Although the radical-mediated hydrogen atom transfer (HAT) process has shown considerable potential in such reactions, it still faces fundamental problems associated with reactivity and selectivity. Herein, we report a convenient and economic approach to site-selective C(sp³)‒H sulfonylation via photo-induced HAT catalysis. Employing a conjugated polycyclic quinone as a direct HAT photocatalyst, commercially available inorganic sulfinates as the sulfonylation source, copper triflate as an inexpensive oxidant, a variety of toluene derivatives and cycloalkanes were converted into biologically and synthetically interesting sulfone products under mild conditions. The mechanistic studies reveal that the reaction sequence involves direct HAT-induced radical formation and a subsequent copper-mediated organometallic process for the C‒S bond formation. This method offers an appealing opportunity to furnish high value-added products from abundant hydrocarbon starting materials and inexpensive reagents.

Key words: Visible light, Photocatalysis, C(sp³)-H functionalization, Sulfonylation, Radical

Shaonan Zhang, Shi Cao, Yu-Mei Lin, Liyuan Sha, Cheng Lu, Lei Gong. Photocatalyzed site-selective C(sp3)‒H sulfonylation of toluene derivatives and cycloalkanes with inorganic sulfinates[J]. Chinese Journal of Catalysis, 2022, 43(3): 564-570.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)63953-0

https://www.cjcatal.com/EN/Y2022/V43/I3/564

Figures/Tables 7

Scheme 1. (a) Representative aryl sulfone-based bioactive molecules; (b) Overview of this work.

Table 1 Optimization of the reaction conditions a.

Entry	Metal salt	PC	T (°C)	Yield ^b (%)
1	Cu(ClO₄)₂∙6H₂O	PC1	20	39
2	Ni(ClO₄)₂∙6H₂O	PC1	20	5
3	Co(ClO₄)₂∙6H₂O	PC1	20	trace
4	Zn(ClO₄)₂∙6H₂O	PC1	20	trace
5	Fe(ClO₄)₂∙H₂O	PC1	20	11
6	CuCl₂∙2H₂O	PC1	20	43
7	CuSO₂∙5H₂O	PC1	20	31
8	Cu(OTf)₂	PC1	20	74
9 ^c	Cu(OTf)₂	PC1	20	71
10 ^d	Cu(OTf)₂	PC1	20	76
11	Cu(OTf)₂	PC2	20	45
12	Cu(OTf)₂	PC3	20	32
13	Cu(OTf)₂	PC4	20	0
14	Cu(OTf)₂	PC1	40	55
15	Cu(OTf)₂	PC1	0	40
16	none	PC1	20	0
17 ^e	none	PC1	20	trace
18 ^f	none	PC1	20	trace
19 ^g	none	PC1	20	trace
20	Cu(OTf)₂	none	20	0
21 ^h	Cu(OTf)₂	PC1	20	0
22 ⁱ	Cu(OTf)₂	PC1	20	trace

Scheme 2. Scope of toluene derivatives and sulfinates. a Reaction in a 1.0 mmol scale.

Scheme 3. C(sp3)-H sulfonylation of cycloalkanes and late-stage functionalization of celestolide.

Scheme 4. (a) Radical trapping experiments; (b) Radical clock experiments; (c) Reactions interfered by other nucleophiles; (d) Direct reaction with a copper sulfinate complex.

Fig. 1. (a) Emission quenching of PC1 with 1-ethyl-naphthalene (1 g); (b) Stern-Volmer plots. I0 and I are respective luminescence intensities in the absence and presence of the indicated concentrations of the corresponding quencher.

Scheme 5. Proposed reaction mechanism.

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