有机氟化物的电化学合成

doi:10.3866/PKU.DXHX202102001

Abstract

Abstract:

Organic fluorides have been widely applied in various spheres, especially in the medical field. However, due to the distinctive reactivity of fluorine, the introduction of fluorine atom has always been a problem in organic chemistry. As a novel synthetic method developed in recent years, organic electrochemical synthesis has greatly expanded the boundaries of organic reactions, which have enabled the development of many efficient and eco-friendly fluorination methods. In this paper, we will focus on these examples of electro-chemical fluorination, and discuss the possible role of electrochemical methods in the field of fluoro-chemistry.

Key words: Electro-organic chemistry, Fluorochemistry, Organic synthesis, Methodology

Zihang Zhang, Sizhe Li, Liyan Kan, Jun Wen, Jiang Bian. Electrosynthesis of Organic Fluorides[J].University Chemistry, 2021, 36(12): 2102001.

Figures/Tables 39

References 46

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Run	β-lactam		Supporting Electrolyte	Product	Yield/%
Run	No.	X	Supporting Electrolyte	Product	Yield/%
1	55a	H	Et₄NF·3HF	56a	42
2	55a	H	Et₃N·3HF	56a	82
3	55b	CH₃	Et₃N·3HF	56b	71
4	55c	Br	Et₃N·3HF	56c	quant.


Run	Dithioacetal			Anode potential/V vs. SCE	Current consumption/electrons molecule^?1	Ar₃N ^a		Yield/% ^b
Run	No.	R	R’	Anode potential/V vs. SCE	Current consumption/electrons molecule^?1	Ar₃N ^a		Yield/% ^b
1	57a	Ph	Ph	1.3	4	58a	59a	58
2	57b	p-FC₆H₄	Ph	1.3	5	58a	59b	83
3	57c	p-FC₆H₄	p-FC₆H₄	1.3	5	58a	59c	58
4	57d	p-ClC₆H₄	p-ClC₆H₄	1.5	5	58b	59d	74
5	57f	n-C₅H₁₁	n-C₅H₁₁	1.5	2.5	58b	59f	trace
6	57e			1.3	5	58a	59e	61
7	57e			1.5	5	58b	59e	76

分子	垂直电离能/(a.u.)	E^OX vs. NHE (实验值)/V	E^OX (计算值)/V
62a	0.22265957	1.80	–
62b	0.21479178	1.60	–
62c	0.19766964	1.13 ^a	–
62d	0.18836738	1.00	–
62e	0.18053204	0.76	–
62f	0.21031914	1.50	–
63a	0.20344247	–	1.492326346
63b	0.20711209	–	1.594207464
63c	0.21327981	–	1.699719982
64	0.24011900	–	2.140778576
62g	–	1.3	–
62h	–	1.74	–

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Electrosynthesis of Organic Fluorides

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Entry	Iodoarene (R=)	Iodoarene (equiv.)	2a ^b/%	3a ^b/%
1	H	1.0	32	16
2 ^c	H	1.0	0	0
3 ^d	H	1.0	6	33
4 ^e	0	7
5	H	2.0	51	3
6 ^f	H	2.0	41	4
7	COMe	2.0	16	30
8	t-Bu	2.0	54	0
9	Me	2.0	55 (53) ^g	0
10 ^h	Me	2.0	30	0
11 ⁱ	Me	2.0	55	0
12 ^j	H	2.0	45	0