Table 3 Arylation of different arenes with 4-iodoanisolea
high regioselectivities in the arylation of substituted arenes.
The excellent chemo- and regioselectivities could be attributed
to the electron configuration and steric hindrance of the micro-
pores (see the ESIw). Moreover, the catalyst is easily recoverable
and reusable (see the ESIw). Our finding might offer a new
strategy to improve the catalytic efficiency of an organic molecule
catalyst by assembling the molecule (or a ligand bearing the same
structure moiety) into a MOF structure.
Entry Arene
Conb (%) Product
Yieldc (%)
56 (62)
(o/m/p = 83/11/6)
1
62
58
This work was supported by the NSFC (20803024,
20936001, and 21073065), DFMEC (200805611045), FRFCU
(2011ZG0009), NSF of Guangdong (S2011020002397,
10351064101000000), the Guangdong provincial engineering
research center for green fine chemicals, and the program for
NCETU (NCET-08-0203).
2
52 (58)
70 (75)
(o/m/p = 90/7/3)
3
75
96 (>99)
(o/m/p = 90/8/2)
4d
>99
Notes and references
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¨
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5
36
30 (36)
96 (>99)
(a/b = 9/91)
6e
>99
72 (75)
(o/m/p = 27/71/2)
7
8
75
63 (67)
(2-Cl/5-Cl = 10/90)
67
70
67 (70)
(2-F/5-F = 13/87)
9
a
Reaction conditions: 1a (0.5 mmol), arenes (4 mL), 130 1C, 72 h.
Determined by GC-MS. Yield determined as a mixture of isomers
b
c
d
e
(GC yield in parenthesis). 140 1C, 96 h. 100 1C, 48 h.
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partner, the b-position arylated product predominated with a
regioselectivity of ca. 91% (entry 6). A high meta selectivity
was obtained when fluorobenzene was used (entry 7). In the
reactions of 1a with electron-rich benzenes, the ortho-arylated
product was observed as a major product (entries 1 and 3).
Moreover, the ortho selectivity was observed to increase
remarkably with an increase in the size of the substituted
group. Substituted toluene at the para-position exhibited
higher regioselectivity than unsubstituted toluene (entries 8
and 9). As shown in Table 3, the substitution of the para-
hydrogen with a chloride atom enhanced the regioselectivity to
the ortho-arylated product (relative to the methyl) from
ca. 83% (for toluene) to 90% (entries 1 and 8). Upon compar-
ing with the reported results (normally with o70% selectivity to
one regioisomer),13,15 it can be seen that the regioselectivities in the
direct arylation of substituted arenes have been improved signifi-
cantly by using the novel catalyst system.
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In summary, we have disclosed a novel heterogeneous
catalysis system for the direct arylation of unactivated arenes
with aryl iodides/bromides by using MOFs as catalyst without
the assistance of any transition metals. Notably, in addition to
excellent chemoselectivities, the MOF catalyst also exhibits
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c
This journal is The Royal Society of Chemistry 2012
Chem. Commun., 2012, 48, 2033–2035 2035