Synthesis of 2,7-Diaryl Substituted Fluorenes and Fluorenones

doi:10.6023/cjoc202311008

Abstract

2,7-Diaryl substituted fluorenes and fluorenones are widely used in fields of organic semiconductor, chemosensor, and metallocene catalysis. Traditional synthesis methods can not meet the requirements of flexible molecular structures and regulation of diverse properties. Aryl-aryl cross coupling reactions based on the catalysis of Pd and Ni complexes have become efficient methods for the preparation of 2,7-diaryl substituted fluorenes and fluorenones. Various types of metal catalysts with phosphine ligands and N-heterocyclic carbene ligands have been applied. The synthetic methods of 2,7-diaryl substituted fluorenones and 2,7-diaryl substituted fluorenes with or without 9-substitutions, and the conditions for the application of Pd and Ni complexes are reviewed. The challenges of various synthetic methods at present are summarized and a brief outlook on possible solutions is provided.

Key words: biaryl, fluorene, fluorenone, luminescent material, metallocene

Cite this article

Yongqing Li, Yuqing Peng, Yucai Cao, Guiping Cao. Synthesis of 2,7-Diaryl Substituted Fluorenes and Fluorenones[J]. Chinese Journal of Organic Chemistry, 2024, 44(5): 1494-1505.

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Entry	X	MY_n	Cat. (loading/mol%)	Base	Solvent	Temp./℃	Time/h	Product (yield^a/%)	Ref.
1	I	B(OH)₂	M2	K₂CO₃	Toluene/Water	Reflux	Over night	11 (60), 12 (40)	[50]
2	I	B(OH)₂	M2 (4.0)	Na₂CO₃	Toluene/Water	110	Over night	2 (93), 3 (80), 4 (93), 5 (90), 6 (77)	[51]
3	I	B(OH)₂	M4·DCM (6.0)	K₂CO₃	THF/Water	Reflux	Over night	1 (78)	[52]
4	Br	ZnCl	M2 (30.0)		THF	Reflux	10	2 (75)	[31]
5	Br	ZnCl	M2 (10.0)		THF	Reflux	6	2 (81)	[49]
6	Br	B(OH)₂	M2 (3.3)	K₂CO₃	Toluene/EtOH	80	8	1 (91)	[2]
7^b	Br	B(OH)₂	M2	K₂CO₃	THF/Water	75	24	8 (82)	[53]
8	Br	B(OH)₂	M3 (20.0)	Cs₂CO₃	Dioxane	80	12	10 (83)	[54]
9	Br	B(OH)₂	M4·DCM (5.0)	Cs₂CO₃	THF/DMF	60	o.n.	1 (83)	[52]
10	Br	B(OH)₂	Pd@DCA-SBA (0.2)	K₂CO₃	EtOH/Water	80	6	1 (86), 9 (82)	[33]
11	Br	B(OBu)₂	M4·DCM (5.0)	Cs₂CO₃	EtOH/DMF	65	o.n.	7 (55)	[5]
12	Cl	ZnCl	M7 (2.0)		THF/NMP	50	3	1 (23 (GC))	[41]
13	Cl	B(OH)₂	M7 (2.0)	K₂CO₃	1,4-Dioxane	60	12	1 (22 (GC))	[41]

Entry	X	MY_n	Cat. (loading/mol%)	Base	Solvent	Temp./℃	Time/h	Product (yield^a/%)	Ref.
1	I	B(OH)₂	M2	K₂CO₃	Toluene/Water	Reflux	Over night	11 (60), 12 (40)	[50]
2	I	B(OH)₂	M2 (4.0)	Na₂CO₃	Toluene/Water	110	Over night	2 (93), 3 (80), 4 (93), 5 (90), 6 (77)	[51]
3	I	B(OH)₂	M4·DCM (6.0)	K₂CO₃	THF/Water	Reflux	Over night	1 (78)	[52]
4	Br	ZnCl	M2 (30.0)		THF	Reflux	10	2 (75)	[31]
5	Br	ZnCl	M2 (10.0)		THF	Reflux	6	2 (81)	[49]
6	Br	B(OH)₂	M2 (3.3)	K₂CO₃	Toluene/EtOH	80	8	1 (91)	[2]
7^b	Br	B(OH)₂	M2	K₂CO₃	THF/Water	75	24	8 (82)	[53]
8	Br	B(OH)₂	M3 (20.0)	Cs₂CO₃	Dioxane	80	12	10 (83)	[54]
9	Br	B(OH)₂	M4·DCM (5.0)	Cs₂CO₃	THF/DMF	60	o.n.	1 (83)	[52]
10	Br	B(OH)₂	Pd@DCA-SBA (0.2)	K₂CO₃	EtOH/Water	80	6	1 (86), 9 (82)	[33]
11	Br	B(OBu)₂	M4·DCM (5.0)	Cs₂CO₃	EtOH/DMF	65	o.n.	7 (55)	[5]
12	Cl	ZnCl	M7 (2.0)		THF/NMP	50	3	1 (23 (GC))	[41]
13	Cl	B(OH)₂	M7 (2.0)	K₂CO₃	1,4-Dioxane	60	12	1 (22 (GC))	[41]

Entry	X	MY_n	Cat. (loading/mol%)	Base	Solvent	Temp./℃	Time/h	Product (yield^a/%)	Ref.
1	I	MgBr	M5 (3.0.)	—	Ethyl ether	Reflux	0.5	13 (90 (GC)), 14 (70 (GC)), 15 (50 (GC)), 16 (70 (GC)), 17 (70 (GC)), 18 (60 (GC))	[26]
2	I	MgBr	M5 (0.8)	—	Ethyl ether	Reflux	0.5	19 (70), 20 (81)	[27]
3	I	B(OH)₂	M1	K₂CO₃	Acetone/Water	Reflux	—	25 (81), 30 (85)	[55]
4	Br	MgBr	M5 (3.0)	—	Ethyl ether	Reflux	0.5	13 (73 (GC))	[26]
5	Br	ZnCl	M2 (10.0)	—	THF	Reflux	4.0	23 (99)	[32]
6	Br^b	B(OH)₂	M2 (13.6)	Na₂CO₃	NMP	100	Over night	37 (44), 38 (20), 39 (16), 40 (28), 41 (7), 42 (18), 43 (7), 44 (8)	[56]
7	Br	B(OH)₂	M2 (5.0)	Na₂CO₃	Toluene/MeOH	—	—	21 (51)	[57]
8	Br^c	B(OH)₂	M2 (2.0)	K₂CO₃	Toluene	85	12.0	22	[11]
9	Br	B(OH)₂	M2 (3.0)	Na₂CO₃	Toluene/Water	Reflex	120.0	26	[58]
10	Br	B(OH)₂	M2 (6.0)	KO^tBu	^tBuOH/DME	Reflux	0.083	17 (40)	[42]
11	Br	B(OH)₂	M4 (10.0)	Cs₂CO₃	DMF	90	16.0	33 (90)	[59]
12	Br	B(OH)₂	M6 (0.05)	K₂CO₃	^tBuOH/MeOH	100	1.5	13 (99)	[40]
13	Br	B(OH)₂	M8 (0.05)	K₂CO₃	EtOH/Water	110	1.0	18 (95), 20 (90), 24 (93), 27 (96), 28 (97), 29 (98), 31 (95), 32 (86)	[60]
14	Br	B(OH)₂	M9 (0.01)	KOH	EtOH/Water	100	1.5	19 (93), 20 (95), 24 (97), 27 (98)	[61]
15	Br	B(OH)₂	M10 (0.0001)	KO^tBu	EtOH/Water	Reflux	0.1	24 (96), 27 (96), 28 (94), 29 (96), 32 (90)	[62]
16	Br	B(OH)₂	M11 (1.5)	K₂CO₃	Water	90	1.5	24 (93), 28 (97), 29 (96)	[63]
17	Br	B(OH)₂	M12 (0.03)	K₂CO₃	EtOH/Water	Reflux	0.5	18 (93), 19 (92), 24 (94), 27 (96), 28 (95), 29 (97), 32 (94)	[43]
18	Br	B(OH)₂	M13 (0.01)	K₂CO₃	EtOH/Water	90	0.5	18 (92), 19(91), 20 (92), 24 (94), 27 (96), 28 (98), 29 (96), 31 (96), 34 (93)	[64]
19	Br	B(pin)	M3 (10.0)	NaOH	Toulene/THF	Reflux	23.0	35 (56), 36 (65)	[12]
20	Cl	MgBr	M7 (2.0)	—	THF	50	3.0	13 (63 (GC))	[41]
21	Cl	ZnCl	M7 (2.0)	—	THF/NMP	50	3.0	13 (77 (GC))	[41]
22	Cl	B(OH)₂	M7 (2.0)	K₂CO₃	1,4-Dioxane	60	12.0	13 (52 (GC))	[41]

Entry	X	MY_n	Cat. (loading/mol%)	Base	Solvent	Temp./℃	Time/h	Product (yield^a/%)	Ref.
1	I	MgBr	M5 (3.0.)	—	Ethyl ether	Reflux	0.5	13 (90 (GC)), 14 (70 (GC)), 15 (50 (GC)), 16 (70 (GC)), 17 (70 (GC)), 18 (60 (GC))	[26]
2	I	MgBr	M5 (0.8)	—	Ethyl ether	Reflux	0.5	19 (70), 20 (81)	[27]
3	I	B(OH)₂	M1	K₂CO₃	Acetone/Water	Reflux	—	25 (81), 30 (85)	[55]
4	Br	MgBr	M5 (3.0)	—	Ethyl ether	Reflux	0.5	13 (73 (GC))	[26]
5	Br	ZnCl	M2 (10.0)	—	THF	Reflux	4.0	23 (99)	[32]
6	Br^b	B(OH)₂	M2 (13.6)	Na₂CO₃	NMP	100	Over night	37 (44), 38 (20), 39 (16), 40 (28), 41 (7), 42 (18), 43 (7), 44 (8)	[56]
7	Br	B(OH)₂	M2 (5.0)	Na₂CO₃	Toluene/MeOH	—	—	21 (51)	[57]
8	Br^c	B(OH)₂	M2 (2.0)	K₂CO₃	Toluene	85	12.0	22	[11]
9	Br	B(OH)₂	M2 (3.0)	Na₂CO₃	Toluene/Water	Reflex	120.0	26	[58]
10	Br	B(OH)₂	M2 (6.0)	KO^tBu	^tBuOH/DME	Reflux	0.083	17 (40)	[42]
11	Br	B(OH)₂	M4 (10.0)	Cs₂CO₃	DMF	90	16.0	33 (90)	[59]
12	Br	B(OH)₂	M6 (0.05)	K₂CO₃	^tBuOH/MeOH	100	1.5	13 (99)	[40]
13	Br	B(OH)₂	M8 (0.05)	K₂CO₃	EtOH/Water	110	1.0	18 (95), 20 (90), 24 (93), 27 (96), 28 (97), 29 (98), 31 (95), 32 (86)	[60]
14	Br	B(OH)₂	M9 (0.01)	KOH	EtOH/Water	100	1.5	19 (93), 20 (95), 24 (97), 27 (98)	[61]
15	Br	B(OH)₂	M10 (0.0001)	KO^tBu	EtOH/Water	Reflux	0.1	24 (96), 27 (96), 28 (94), 29 (96), 32 (90)	[62]
16	Br	B(OH)₂	M11 (1.5)	K₂CO₃	Water	90	1.5	24 (93), 28 (97), 29 (96)	[63]
17	Br	B(OH)₂	M12 (0.03)	K₂CO₃	EtOH/Water	Reflux	0.5	18 (93), 19 (92), 24 (94), 27 (96), 28 (95), 29 (97), 32 (94)	[43]
18	Br	B(OH)₂	M13 (0.01)	K₂CO₃	EtOH/Water	90	0.5	18 (92), 19(91), 20 (92), 24 (94), 27 (96), 28 (98), 29 (96), 31 (96), 34 (93)	[64]
19	Br	B(pin)	M3 (10.0)	NaOH	Toulene/THF	Reflux	23.0	35 (56), 36 (65)	[12]
20	Cl	MgBr	M7 (2.0)	—	THF	50	3.0	13 (63 (GC))	[41]
21	Cl	ZnCl	M7 (2.0)	—	THF/NMP	50	3.0	13 (77 (GC))	[41]
22	Cl	B(OH)₂	M7 (2.0)	K₂CO₃	1,4-Dioxane	60	12.0	13 (52 (GC))	[41]

Entry	X	MY_n	Cat. (loading/mol%)	Base	Solvent	Temp./℃	Time/h	Product (yield^a/%)	Ref.
1	I	B(OH)₂	M2 (8.0)	K₂CO₃	Toluene/Water	Reflux	40	59 (85), 83 (80), 88 (69), 91 (75), 101(82), 107(74)	[95]
2	Br	ZnCl	M2 (1.5)	—	THF	55	16	60 (77)	[45]
3	Br	B(OH)₂	M1 (5.0)	K₂CO₃	ⁱPrOH/Water	85	24	93 (67)	[96]
4	Br	B(OH)₂	M1 (5.0)	K₂CO₃	EtOH/Water	85	24	90 (77)	[96]
5	Br	B(OH)₂	M1	K₂CO₃	Acetone/Water	Reflux	—	74 (58), 75 (38)	[55]
6	Br	B(OH)₂	M1/P^tBu₃ (3.0)	K₂CO₃	THF	70	24	58 (43)	[91]
7	Br	B(OH)₂	M2 (2.5)	Na₂CO₃	Toluene/Water	Reflux	48	57 (76)	[90]
8	Br	B(OH)₂	M2 (2.0)	Na₂CO₃	Toluene/Water	Reflux	24	103 (65)	[83]
9	Br	B(OH)₂	M2 (3.0)	Na₂CO₃	Toluene/Water	Reflux	72	104 (76)	[24]
10	Br	B(OH)₂	M2 (10.0)	Na₂CO₃	toluene/EtOH/Water	Reflux	24	54, 78, 79, 85, 87	[82]
11	Br	B(OH)₂	M2 (3.6)	K₂CO₃	toluene/EtOH/Water	Reflux	24	46 (60), 49 (74), 51 (74), 61, 84	[94]
12	Br	B(OH)₂	M2 (20.0)	Na₂CO₃	toluene/EtOH/Water	Reflux	24	89 (77)	[93]
13	Br	B(OH)₂	M2 (4.0)	Na₂CO₃	toluene/EtOH/Water	Reflux	4	86 (65)	[97]
14	Br	B(OH)₂	M2 (5.0)	K₂CO₃	ⁱPrOH/Water	85	24	76 (42)	[92]
15	Br	B(OH)₂	M2 (15.0)	K₂CO₃	THF/Water	66	9	62 (81)	[20]
16	Br^b	B(OH)₂	M2	K₂CO₃	THF/Water	70	24	92 (85)	[81]
17	Br	B(OH)₂	M2 (10.0)	Na₂CO₃	THF/Water	reflux	Over night	69 (67)	[1]
18	Br	B(OH)₂	M2 (3.0)	K₂CO₃	1,4-Dioxane	110	24	77 (57)	[19]
19	Br	B(OH)₂	M3 (4.0)	KOH	THF/Water	80	24	50 (65), 55 (83), 82 (61), 90 (77), 97 (71), 98 (82)	[13,98]
20	Br	B(OH)₂	M4 (10.0)	Cs₂CO₃	DMF	90	16	99 (70)	[59]
21	Br	B(OH)₂	M9 (0.01)	KOH	EtOH/Water	100	1.5	45 (95), 47 (94), 63 (92), 81 (94), 94 (97), 95 (98), 102 (96), 105 (96)	[61]
22	Br	B(OH)₂	M10 (0.0001)	KO^tBu	EtOH/Water	Reflux	—	45 (98), 48 (93), 64 (94), 94 (99), 95 (97), 96 (94), 105 (97), 106 (93)	[62]
23	Br	B(OH)₂	M11 (1.5)	K₂CO₃	Water	90	1.5	45 (96), 48 (94), 95 (98), 96 (95), 105(97), 106(92)	[63]
24	Br	B(OH)₂	M12 (0.03)	K₂CO₃	EtOH/Water	Reflux	0.5	65(93), 67(91), 68(90)	[43]
25	Br	B(OH)₂	M14 (0.05)	K₃PO₄•7H₂O	EtOH/Water	60	1	45 (92), 63 (95), 66 (93), 80 (93), 81 (94), 94 (96), 95 (94), 105 (95)	[44]
26	Br	B(OBu)₂	M4·DCM (2.0)	Cs₂CO₃	DMF/EtOH	65	Over night	100 (39)	[5]
27	Br	B(pin)	M2 (4.0)	K₂CO₃	Toluene/Water	Reflux	24	58 (66)	[8]
28	Cl	MgBr	M7 (2.0)	—	THF	50	3	56 (69 (GC))	[41]
29	Cl	ZnCl	M7 (2.0)	—	THF/NMP	50	3	56 (72 (GC))	[41]
30	Cl	B(OH)₂	M7 (2.0)	K₂CO₃	1,4-Dioxane	60	12	56 (34 (GC))	[41]

2,7-二芳基取代芴/芴酮的合成