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DOI: 10.1055/s-0030-1258059
Efficient Borylation of Reactive Aryl Halides with MPBH (4,4,6-Trimethyl-1,3,2-dioxaborinane)
Publikationsverlauf
Publikationsdatum:
19. August 2010 (online)
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Abstract
The combination of 4,4,6-trimethyl-1,3,2-dioxaborinane, a particularly stable and inexpensive borylation reagent, and Buchwald’s palladium catalyst provides a simple, fast, cost-effective borylation of electron-rich, reactive iodides, bromides, and triflates to produce stable, easily purified boronic esters.
Key words
boron - palladium - catalysis - arylboronic - Suzuki
- Supporting Information for this article is available online:
- Supporting Information
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References and Notes
Preparation of
MPBH
Under a well-ventilated fume hood (H2 evolution),
a 100 mL flask equipped with a Claisen distillation head was charged with
10% Pd/C (320 mg) and anhyd dioxane (10 mL). The flask
was flushed with nitrogen and freshly distilled 2-methyl-2,4-pentanediol
(50 mmol, 6.4 g) in dioxane (10 mL) was added. A solution of N,N-diethylaniline-borane
(60 mmol, 9.78 g) in dioxane (10 mL) was added at 20 ˚C
over 30 min. The reaction mixture was stirred for an additional
30 min at 20 ˚C. Low pressure distillation gave
neat MPBH (4.8 g, 75%, bp 45 ˚C/0.05
bar).
Our attempts to use N,N-diethylaniline as the base in subsequent borylations failed.
10
Typical Procedure
for the Borylation
An oven-dried Schlenk vessel (or
a 10 mL microwaves vial) was charged with Pd2
(dba)3 (2.3
mg, 2.5 µmol, described as 0.5% in Table
[¹]
) and CyJohnPhos (3.5 mg,
10 µmol, always 2 equiv/Pd) and placed under an
atmosphere of Argon. Anhydrous dioxane (0.6 mL), the aryl halide
(0.5 mmol), Et3N (152 mg, 1.5 mmol) and MPBH (96 mg,
0.75 mmol) were introduced (solid aryl halides were added along
with the other solid reagents). The reaction mixture was then heated
at the indicated temperature until the aryl halide has been completely
consumed as determined by gas chroma-tography. The reaction was
allowed to cool to r.t., and filtered through a short pad of Celite
(eluent Et2O). The eluate was concentrated and the crude
material purified by flash chromatography on silica gel. Products 2a-j
²,³, 3g
¹b and 3h
¹i have been previously
described.
4,4,6-Trimethyl-2-naphthalen-2-yl[1,3,2]dioxaborinane (2g)
¹H
NMR (400 MHz, CDCl3): δ = 8.34 (s,
1 H), 7.89-7.85 (m, 2 H), 7.82-7.76 (m, 2 H),
7.48-7.40 (m, 2 H), 4.38 (dqd, J = 11.8,
6.2, 2.9 Hz, 1 H), 1.87 (dd, J = 13.7,
2.9 Hz, 1 H), 1.62 (dd, J = 13.7,
11.8 Hz, 1 H), 1.41 (s, 3 H), 1.39 (s, 3 H), 1.38 (d, J = 6.2 Hz,
3 H) ppm. ¹³C NMR (75.5 MHz, CDCl3): δ = 134.8
(2×), 132.99, 130.14, 128.68, 127.67, 129.5 (v br, CB),
126.62, 126.39, 125.44, 71.16, 65.14, 46.15, 31.38, 28.27, 23.30
ppm. ¹¹B NMR (128 MHz, CDCl3): δ = 27.10. IR
(neat): 3053, 2972, 2932, 2911, 1630, 1598, 1503, 861, 823, 765,
746, 685 cm-¹. MS (EI, 70 eV): m/z (%) = 255
(26), 254 (100), 253 (28).
See Supporting Information for a detailed table of these experiments.