Study on FeCl3-Mediated Reaction of Aryl Boronic Esters with Electrophiles

doi:10.6023/cjoc202506018

Abstract

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

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Lihua Cui, Yatong Li, Qifeng Wang. 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

三氯化铁促进的芳基硼酸酯与亲电试剂的反应研究

Study on FeCl₃-Mediated Reaction of Aryl Boronic Esters with Electrophiles

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