Chemoselective Electro-oxidation of Allyl Arene to Ester

doi:10.6023/cjoc202309019

Abstract

An electrochemical C—H and C—C bond esterification reaction with allyl arene as a substrate is reported. This oxidation takes place selectively at the benzyl^＋allyl C—H site instead of other benzylic C—H groups. Since the reaction does not require acid/base catalysis for esterification, tertiary alcohol is suitable for the synthesis of the corresponding ester. In addition, side reactions such as transesterification can be avoided with this neutral protocol.

Key words: allyl, benzyl, electrochemistry, esterification

Cite this article

Mengfan Li, Xu Cheng. Chemoselective Electro-oxidation of Allyl Arene to Ester[J]. Chinese Journal of Organic Chemistry, 2024, 44(3): 1005-1012.

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Fig. & Tab. 7

Scheme 1. Electrochemical oxidation of benzylic C—H and allyl arene

Scheme 2. Substrate scope of electrochemical oxidative esterification of allyl arene (part 1) Reaction conditions: 1a (0.65 mmol, 1.0 equiv.), 2 (3 mL), nBu4NBF4 (2.0 equiv.), MeCN (5 mL), under air conditions for 3~4 h, cell voltage 6 V or constant current 120 mA/cm3, isolated yield.

Scheme 3. Substrate scope of electrochemical oxidative esterification of allyl arene (part 2) Reaction conditions: 1 (0.65 mmol, 1.0 equiv.), MeOH (2a, 3 mL), nBuNBF4 (2.0 equiv.), MeCN (5 mL), under air conditions for 3~4 h, cell voltage 6 V or constant current 120 mA/cm3, isolated yield.

Entry	Electrolyte	Electrodes	Solvent	Yield^b/%
1	ⁿBu₄NBF₄	GF anode, GF cathode	MeCN	33
2	ⁿBu₄NBF₄	GF anode, Pt cathode	MeCN	89 (83)
3	ⁿBu₄NClO₄	GF anode, Pt cathode	MeCN	13
4	ⁿBu₄NOH	GF anode, Pt cathode	MeCN	8
5	ⁿBu₄NBr	GF anode, Pt cathode	DMF	40
6	ⁿBu₄NBF₄	GF anode, Pt cathode	Acetone	47
7^c	ⁿBu₄NBF₄	GF anode, Pt cathode	MeCN	21
8^d	ⁿBu₄NBF₄	GF anode, Pt cathode	MeCN	83
9^e	ⁿBu₄NBF₄	GF anode, Pt cathode	MeCN	63
10^f	ⁿBu₄NBF₄	GF anode, Pt cathode	MeCN	35
11^g	ⁿBu₄NBF₄	GF anode, Pt cathode	MeCN	60
12^h	ⁿBu₄NBF₄	GF anode, Pt cathode	MeCN	Trace
13	ⁿBu₄NBF₄	Pt anode, Pt cathode	MeCN	17
14	ⁿBu₄NBF₄	Graphite plate anode, Pt cathode	MeCN	Trace

Table 1. Optimization of the electrochemical oxidative esterification of allyl arenea

Scheme 4. Exploration of the synthetic information of phenyl allyl esterification Reaction conditions: 4~6 (0.65 mmol, 1.0 equiv.), MeOH (2a, 3 mL), nBuNBF4 (2.0 equiv.), MeCN (5 mL), under air conditions for 2.0~4.5 h, constant current 120 mA/cm3, isolated yield. 1a (5 mmol, 1.0 equiv.), MeOH (2a, 15 mL), nBuNBF4 (2.0 equiv.), MeCN (25 mL), under air conditions for 6 h, cell voltage 6 V, isolated yield.

Figure 1. CV analysis of the substrate 1a and the contrast

Scheme 5. Study on intermediate to elucidate the reaction pathway

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