三氯化铁促进的芳基硼酸酯与亲电试剂的反应研究

doi:10.6023/cjoc202506018

摘要/Abstract

提出了通过三价铁与有机硼试剂反应得到有机铁中间体的简便方法, 并研究了该中间体与各类亲电试剂的反应. 研究表明, 有机硼的频哪醇结构对三价铁参与的C—B键切断至关重要, 所生成的有机铁中间体稳定性低, 有较弱的亲核反应能力, 与酰氯、酸酐、异氰酸酯等能够偶联.

关键词: 有机硼, 有机铁, 偶联, C—B切断

A concise approach to the synthesis of organoiron intermediate from organoboron and Fe(III) has been developed, and the reactivity of the intermediate with a series of electrophiles has been investigated. The results revealed that pinacol substituent of organoboron is crucial for C—B cleavage. The resulted organoiron intermediate is not stable, with weak nucleophicility. The coupling reactions of organoiron intermediate with acyl chlorides, anhydrides, isocyanates have been performed.

Key words: organoiron, organoboron, coupling, C—B cleavage

引用此文

崔利华, 李亚彤, 王奇峰. 三氯化铁促进的芳基硼酸酯与亲电试剂的反应研究[J]. 有机化学, 2026, 46(1): 199-206.

Cui Lihua, Li Yatong, Wang Qifeng. Study on FeCl₃-Mediated Reaction of Aryl Boronic Esters with Electrophiles[J]. Chinese Journal of Organic Chemistry, 2026, 46(1): 199-206.

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Entry	[M] (equiv.)	Solvent	T/℃	t/min	Yield^a/%
1	FeCl₃ (2.0)	CH₂Cl₂	100	5	84
2	AlCl₃ (2.0)	CH₂Cl₂	100	5	15
3	CuCl₂ (2.0)	CH₂Cl₂	100	30	N.D.^b
4	Fe₂(SO₄)₃ (1.0)	CH₂Cl₂	100	180	7
5	Fe(acac)₃ (2.0)	CH₂Cl₂	100	60	N.D.
6	Fe(OAc)₂ (2.0)	CH₂Cl₂	100	60	N.D.
7	FeCl₂ (2.0)	CH₂Cl₂	100	60	N.D.
8	Fe₂O₃ (2.0)	CH₂Cl₂	100	60	N.D.
9	FeCl₃ (2.0)	THF	100	120	N.D.
10	FeCl₃ (2.0)	DMF	100	120	N.D.
11	FeCl₃ (2.0)	CHCl₃	100	90	61
12	FeCl₃ (1.0)	CH₂Cl₂	100	90	18
13	FeCl₃ (2.0)	CH₂Cl₂	25	30	87
14^c	FeCl₃ (2.0)	CH₂Cl₂	25	60	49
15^d	FeCl₃ (2.0)	CH₂Cl₂	25	60	<5

Entry	[M] (equiv.)	Solvent	T/℃	t/min	Yield^a/%
1	FeCl₃ (2.0)	CH₂Cl₂	100	5	84
2	AlCl₃ (2.0)	CH₂Cl₂	100	5	15
3	CuCl₂ (2.0)	CH₂Cl₂	100	30	N.D.^b
4	Fe₂(SO₄)₃ (1.0)	CH₂Cl₂	100	180	7
5	Fe(acac)₃ (2.0)	CH₂Cl₂	100	60	N.D.
6	Fe(OAc)₂ (2.0)	CH₂Cl₂	100	60	N.D.
7	FeCl₂ (2.0)	CH₂Cl₂	100	60	N.D.
8	Fe₂O₃ (2.0)	CH₂Cl₂	100	60	N.D.
9	FeCl₃ (2.0)	THF	100	120	N.D.
10	FeCl₃ (2.0)	DMF	100	120	N.D.
11	FeCl₃ (2.0)	CHCl₃	100	90	61
12	FeCl₃ (1.0)	CH₂Cl₂	100	90	18
13	FeCl₃ (2.0)	CH₂Cl₂	25	30	87
14^c	FeCl₃ (2.0)	CH₂Cl₂	25	60	49
15^d	FeCl₃ (2.0)	CH₂Cl₂	25	60	<5

Entry	Electrophile	Yield^b/% of 2	Entry	Yield^b/% of 4
1	H₂O	87	6	51
2^c	H₂O	85^d	7	68
3	H₂O	64^e	8	63
4^f	H₂O	58^d	9	66
5^g	H₂O	52^d	10	86

Entry	Electrophile	Yield^b/% of 2	Entry	Yield^b/% of 4
1	H₂O	87	6	51
2^c	H₂O	85^d	7	68
3	H₂O	64^e	8	63
4^f	H₂O	58^d	9	66
5^g	H₂O	52^d	10	86