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Simple and Green Preparation of Tetraalkoxydiborons and Diboron

Diolates from Tetrahydroxydiboron
Ryan M. Fornwald,† Anshu Yadav,† Jose R. Montero Bastidas, Milton R. Smith, III,*
and Robert E. Maleczka, Jr.*
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ABSTRACT: Tetraalkoxydiborons can be easily prepared by acid-catalyzed

reactions of tetrahydroxydiboron or its anhydride with trialkyl orthoformates.
Addition of diols to these reaction mixtures afforded diboron diolates in high
yield. In both cases, removal of volatile byproducts is all that is required for the
Downloaded via 77.65.81.89 on April 19, 2025 at 12:01:53 (UTC).

isolation of the diboron. These methods constitute a convenient alternative to

previous preparations from tetrakis (dimethylamino) diboron and tetrahy-
droxydiboron.

1. INTRODUCTION 2. RESULTS AND DISCUSSION

Diboron diolates have broad applications in synthesis,1−5 and Inspired by a previous report for the preparation of thiophene
while they are generally bench-stable compounds, their boronic ester from thiophene boronic acid by reaction with
preparation can be tedious. Boron−boron bonds are trimethyl orthoformate in the presence of an acid catalyst,23 we
commercially prepared via the Wurtz coupling of halobis have developed an exceptionally fast and convenient method
(dialkylamino) boranes (Scheme 1a).6,7 While tetrakis for the preparation of diboron diolates and tetraalkoxydiborons
(Scheme 2).
Scheme 1. Previous Work The acetyl chloride-catalyzed reaction of B2(OH)4 (1) with
CH(OMe)3 is complete within minutes at room temperature,
is not particularly air-sensitive, and offers a visual indicator of
completion, producing a homogeneous solution (B2(OMe)4
(2), MeOH, and methyl formate) after consumption of
starting material. The diol is then added, the solution stirred
briefly, and solvent removed in vacuo to afford the desired
diboron in high yield, typically without a need for further
purification.
A variety of diboron diolates (3−16) were prepared on a
gram scale (Scheme 3) by using this methodology. Reactions
with aliphatic 1,2-diols (3−9), aliphatic 1,3-diols (10−13), and
phenols such as catechol or 2-hydroxybenzyl alcohol (14−15)
were successful as well as 1,2-diaminobenzene (16) formed the
desired product. Conversion was low with diisopropyl tartrate,
and perfluoropinacol failed to afford any product. Attempts to
separate B2(OMe)4 (2) from the MeOH byproduct by
(dialkylamino) diborons also have applications in syn- distillation were unsuccessful.
thesis,8−10 diboron diolates are far more widely used.1−5 B2eg2 (3) and commonly used B2pin2 appear as white solids
Their direct preparation from tetrakis (dialkylamino) diborons at room temperature, whereas synthetic B2pg2 (4) is a colorless
liquid. B2pg2 was made starting with a racemic mixture of
requires the use of a dry solution of HCl in Et2O at −78 °C,
filtration of dialkylammonium hydrochloride salts, then
distillation, sublimation, or crystallization of the diboron Received: December 30, 2023
diolate.6,7 However, B2(OH)4 (1) is also readily prepared via Revised: March 27, 2024
hydrolysis of tetrakis (dialkylamino)diboron.11 Diboron Accepted: April 5, 2024
diolates can also be synthesized by stirring a heterogeneous Published: April 19, 2024
mixture of B2(OH)4 with a diol and MgSO4 for 24 h (Scheme
1b).12−22
© 2024 The Authors. Published by
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6048 J. Org. Chem. 2024, 89, 6048−6052
The Journal of Organic Chemistry pubs.acs.org/joc Article

Scheme 2. This Work Scheme 3. Reaction Scopea

propylene glycol that should lead to a mixture of diastereomers

and explain its liquid phase (Figure 1). In fact, when the pure
enantiomer (S)-propylene glycol is used as the starting diol,
(S,S)-B2pg2 is obtained as a crystalline solid. To measure the
ratio of the stereoisomers in the mixture of B 2 pg 2
diastereomers, we added NMR shift reagents. The methyl
groups in the B2pg2 mixture appear as one peak, which splits
into different ones after the addition of the NMR shift reagent.
a
As expected, the two B2pg2 diastereomers are present in a Isolated yield. bDistilled under vacuum. cIsolated by DCM/water
50:50 mixture corresponding to the meso isomer (S,R)-B2pg2 extraction.
and an equimolar mixture of the enantiomers (S,S)-B2pg2 and
(R,R)-B2pg2. 4. EXPERIMENTAL SECTION
Interestingly, the anhydride of B2(OH)4 can be prepared
4.1. General Information. All diols were purchased from Sigma
quantitatively by heating under vacuum for several hours, except ethane-1,2-diol and 3-methylbutane-1,3-diol, which were
generating (B2O2)n (17) as a hard white solid (Scheme 2).11,24 purchased from Fischer Chemicals and Oakwood Chemical
This material failed to react with CH(OMe)3 in the presence respectively. Benzene-1,2-diamine was purchased from Eastman
of catalytic AcCl, but did so with dry HCl in Et2O (Scheme 4). Chemicals. All commercial chemicals were used as received unless
These reactions are much slower than those with B2(OH)4 (1) otherwise indicated. 1H, 13C, and 11B NMR spectra were recorded on
and require gentle heating. Removal of residual (B2O2)n by a Varian 500 MHz DD2 Spectrometer equipped with a
1
filtration, and Et2O and methyl formate by vacuum distillation H−19F/15N−31P 5 mm Pulsed Field Gradient (PFG) probe.
with a water aspirator afforded B2(OMe)4 in good yield and Chemical shifts are reported as parts per million (ppm). Splitting
91% purity (containing 4% methyl formate, 2% MeOH, and patterns are designated as singlet (s), doublet (d), triplet (t), quartet
3% Et2O). This is a simple alternative to previous methods for (q), doublet of doublet (dd), and doublet of doublet of doublets
(ddd). NMR spectra were processed for display using the MNova
its synthesis from tetrakis(dialkylamino)diborons.6 software program with only phasing and baseline corrections applied.
We also attempted to prepare B2(OEt)4 via this method and High-resolution mass spectra (HRMS) were recorded on a Leco GC-
obtained a mixture whose primary spectral features were ToF spectrometer. All reactions were carried out under a nitrogen
consistent with its structure. However, our assignment is not atmosphere in oven-dried glassware. Anhydrous dichloromethane was
secure due to the complexity of the spectra. (Caution: unlike obtained from commercial sources and was used without further
B2(OMe)4, the reaction of B2(OEt)4 with air is spontaneous and purification. Boron monoxide ((B2O2)n) was prepared as previously
very exothermic!) described in the literature.11,24 The reported yields describe the
results of a single experiment.
3. CONCLUSIONS 4.2. General Experimental Procedure. An oven-dried round-
bottom flask was charged with B2(OH)4 (1.0 equiv) and CH(OMe)3
In conclusion, we have developed a simple, convenient, and (4.0 equiv) and a stir bar. AcCl was added (0.02 equiv), the vessel was
high yielding method for the preparation of both diboron flushed with N2 and sealed with a silicone septum, and the mixture
diolates and tetraalkoxydiborons using bench-stable B2(OH)4 was stirred rapidly at room temperature until all solid material had
as a universal precursor. dissolved (5 min or less, determined by stir rate and the grain size of

6049 https://doi.org/10.1021/acs.joc.3c02992
J. Org. Chem. 2024, 89, 6048−6052
The Journal of Organic Chemistry pubs.acs.org/joc Article

were inconsistent with literature values as impurities were present in

the literature spectrum.16 1H NMR (500 MHz, CDCl3):16 δ 4.18 (s,
8H); 13C NMR (126 MHz, CDCl3):16 δ 65.7; 11B NMR (160 MHz,
CDCl3):16 δ 30.82. GC-MS (EI) m/z calcd for C4H8B2O4 [M]+
142.06, found: 142.1.
4.2.3. 4,4′-Dimethyl-2,2′-bi(1,3,2-dioxaborolane) (B2pg2) (4). The
title compound was prepared from B2(OH)4 (2.24 g, 25 mmol),
CH(OMe)3 (10.94 mL, 100 mmol), AcCl (18 μL, 0.25 mmol), and
propylene glycol (3.65 mL, 50 mmol) according to the general
procedure. The mixture was concentrated and then distilled at 0.07
torr to afford 3.64 g (86%) of the title compound as a colorless oil.
The title compound has been reported before, but no spectroscopic
data were provided. 1H NMR (500 MHz, CDCl3): δ 4.57−4.50 (m,
2H), 4.26 (dd, J = 8.0, 0.9 Hz, 2H), 3.70 (ddd, J = 8.3, 7.4, 1.0 Hz,
2H), 1.31 (dd, J = 6.2, 0.5 Hz, 6H); 13C{1H} NMR (126 MHz,
CDCl3): δ 73.6, 73.6, 72.1, 21.8; 11B NMR (160 MHz, CDCl3): δ
30.7. HRMS (GC/ToF) m/z calc for C6H12B2O4 [M]+ 170.0922,
found: 170.0911.
4.2.4. (4S,4′S) 4,4′-Dimethyl-2,2′-bi(1,3,2-dioxaborolane) ((S,S)-
B2pg2) (5). The title compound was prepared from B2(OH)4 (2.24 g,
25 mmol), CH(OMe)3 (10.94 mL, 100 mmol), AcCl (18 μL, 0.25
mmol), and (S)-propylene glycol (3.65 mL, 50 mmol) according to
the general procedure. This procedure afforded 4.04 g (95%) of the
title compound as a white solid: mp = 152−154 °C. 1H NMR (500
MHz, CDCl3): δ 4.63−4.46 (m, 2H), 4.24 (dd, J = 8.2, 1.0 Hz, 2H),
3.68 (dd, J = 7.4, 1.5 Hz, 2H), 1.29 (d, J = 6.3 Hz, 6H). 13C NMR
Figure 1. 1H NMR spectra of a mixture of B2pg2 with NMR shift (126 MHz, CDCl3): δ 73.5, 72.1, 21.8. 11B NMR (160 MHz, CDCl3):
reagent Eu(fod)3 and optically active NMR chiral shift reagent δ 30.66. HRMS (GC/ToF) m/z calc for C6H12B2O4 [M]+ 170.0922,
Eu(hfc)3. found: 170.0664.
4.2.5. 4,4′-Diethyl-2,2′-bi(1,3,2-dioxaborolane) (B2bg2) (6). The
Scheme 4. Synthesis of Tetramethoxydiboron title compound was prepared from B2(OH)4 (2.24 g, 25 mmol),
CH(OMe)3 (10.94 mL, 100 mmol), AcCl (18 μL, 0.25 mmol), and
1,2-butanediol (4.5 mL, 50 mmol) according to the general
procedure. This procedure afforded 4.85 g (98%) of the title
compound as a colorless oil. 1H NMR (500 MHz, CDCl3): δ 4.39−
4.33 (m, 2H), 4.24 (dd, J = 8.3, 0.5 Hz, 2H), 3.78 (ddd, J = 8.9, 7.4,
1.7 Hz, 2H), 1.70−1.53 (m, 4H), 0.95 (t, J = 7.4 Hz, 6H). 13C{1H}
NMR (126 MHz, CDCl3): δ 78.6, 70.4, 29.0, 29.0, 9.3. 11B NMR
the B2(OH)4). The diol was then added, and the mixture was stirred (160 MHz, CDCl3): δ 30.65. HRMS (GC/ToF) m/z calc for
for 30 min. Solvent was removed in vacuo via rotary evaporation and C8H16B2O4 [M]+ 198.1235, found: 198.1224.
then under high vacuum to afford the title compound. 4.2.6. 4,4,4′,4′-Tetramethyl-2,2′-bi(1,3,2-dioxaborolane) (7).
4.2.1. Tetramethoxydiboron (B2(OMe)4) (2). A 1 dram vial was B2(OH)4 (896 mg, 10 mmol) and CH(OMe)3 (4.24 g, 40 mmol)
charged with a stir bar, (B2O2)n (268 mg, 5 mmol), CH(OMe)3 (1.15 were stirred in a Schlenk flask and the suspension was degassed with
mL, 10.5 mmol), and 2.0 M HCl in Et2O (0.25 mL, 0.5 mmol). The N2 for 15 min. One drop of acetyl chloride, AcCl, was added, and the
vial was flushed with N2 and capped and then stirred at 40 °C in an oil mixture became a homogeneous solution. 2-methyl-1,2-propandiol
bath for 48 h. The cap was replaced with a septum and connected to a (mpg, 1.80 g, 20 mmol) was added, and the reaction was stirred at
water aspirator by a length of PTFE tubing. HCO2Me and Et2O were room temperature overnight. The mixture was concentrated and then
removed via vacuum distillation at room temperature, gradually distilled under reduced pressure to yield 730 mg of the title
raising the temperature over 1 h to 40 °C in an oil bath. The compound as a colorless oil (37% yield). The 1H NMR spectrum is
remaining liquid was then filtered through glass wool under a N2 inconsistent with literature due to different field strengths. However,
atmosphere. This procedure afforded 608 mg of the title compound in our 1H, 13C, and 11B are self-consistent.25 1H NMR (500 MHz,
91% purity (containing 4% methyl formate, 2% methanol, 3% diethyl CDCl3): δ 3.89 (s, 4H), 1.36 (s, 12H). 13C{1H} NMR (126 MHz,
ether) as a colorless oil for an overall yield of 553 mg (76%). The CDCl3): δ 80.5, 77.4, 28.6. 11B NMR (160 MHz, CDCl3): δ 30.80.
relative proportions of each component were estimated via spectral GC-MS (EI) m/z calcd for C8H16B2O4 [M]+ 198.1, found: 198.1.
deconvolution using the line fitting protocol in Mnova 14.2.0 4.2.7. (4R,4′R,5R,5′R)-4,4′,5,5′-Tetramethyl-2,2′-bi(1,3,2-dioxa-
(Mestrelab Research, S.L.; Santiago de Compostela, Spain) using borolane) (8). B2(OH)4 (896 mg, 10 mmol) and CH(OMe)3 (4.24
Gaussian/Lorentzian peak shapes and simulated annealing. Spectral g, 40 mmol) were stirred in a Schlenk flask, and the suspension was
data are for the title compound. 1H NMR (500 MHz, CDCl3): δ 3.62 degassed with N2 for 15 min. One drop of acetyl chloride, AcCl, was
(s, 12H); 13C{1H} NMR (126 MHz, CDCl3): δ 52.1; 11B NMR (160 added, and the mixture became a homogeneous solution. (2R,3R)-
MHz, CDCl3): δ 31.2. (For NMR spectra in C7D8 see Braunschweig, butanediol (1.80 g, 20 mmol) was added, and the reaction was stirred
H.; Damme, A. Thermodynamic control of oxidative addition and at room temperature overnight. The mixture was concentrated and
reductive elimination processes in cis-bis(dimethoxyboryl)-bis- then distilled under reduced pressure to yield 820 mg of the title
(tricyclohexylphosphine)platinum(II). Chem. Commun. 2013, 49 compound as a colorless oil (41% yield) that matched previously
(45), 5216−5218). reported spectra.25 1H NMR (500 MHz, CDCl3): δ 3.99−3.93 (m,
4.2.2. 2,2′-Bi(1,3,2-dioxaborolane) (B2eg2) (3). The title com- 4H), 1.28−1.23 (m, 12H). 13C{1H} NMR (126 MHz, CDCl3): δ
pound was prepared from B2(OH)4 (2.24 g, 25 mmol), CH(OMe)3 80.3, 20.9. 11B NMR (160 MHz, CDCl3): δ 30.5. GC-MS (EI) m/z
(10.94 mL, 100 mmol), AcCl (18 μL, 0.25 mmol), and ethylene calcd for C8H16B2O4 [M]+ 198.1, found: 198.1.
glycol (2.8 mL, 50 mmol) according to the general procedure. This 4.2.8. (4R,4′R,5R,5′R)-4,4′,5,5′-Tetraphenyl-2,2′-bi(1,3,2-dioxa-
procedure afforded 3.22 g (91%) of the title compound as a white borolane) (9). The title compound was prepared from B2(OH)4
solid: mp = 163−164 °C (lit mp = 159−160 °C16). 1H and 13C, data (0.56 g, 6.25 mmol), CH(OMe)3 (2.73 mL, 25 mmol), 2 mol % AcCl

6050 https://doi.org/10.1021/acs.joc.3c02992
J. Org. Chem. 2024, 89, 6048−6052
The Journal of Organic Chemistry pubs.acs.org/joc Article

(4.5 μL, 0.0625 mmol), and (1R,2R)-1,2-diphenylethylene glycol 4.2.14. 4H,4′H-2,2′-Bibenzo[d][1,3,2]dioxaborinine (15). The title
(2.67 g, 12.5 mmol) according to the general procedure. This compound was prepared from B2(OH)4 (1, 1.12 g, 12.5 mmol),
procedure afforded 2.57 g (92%) of the title compound as a pale pink- CH(OMe)3 (5.47 mL, 50 mmol), AcCl (9 μL, 0.125 mmol), and 2-
white solid: mp = 191−194 °C. 1H and 13C NMR data were hydroxybenzyl alcohol (3.1 g, 25 mmol) according to the general
consistent with literature values.26 1H NMR (500 MHz, CDCl3):26 δ procedure. DCM/water extraction was performed to obtain a pure
7.45−7.35 (m, 20H), 5.30 (s, 4H); 13C{1H} NMR (126 MHz, compound. This procedure afforded 2.72 g (82%) of the title
CDCl3):26 δ 139.9, 128.9, 128.5, 126.1, 86.8; 11B NMR (160 MHz, compound as an orange solid (mp = 160−164 °C) that matched
CDCl3):26 δ 31.46. previously reported data.25 1H NMR (500 MHz, CDCl3):25 δ 7.23−
4.2.9. 4,4′-Dimethyl-2,2′-bi(1,3,2-dioxaborinane) (10). The title 7.19 (m, 2H), 7.07 (dd, J = 8.0, 0.9 Hz, 2H), 7.03 (td, J = 7.4, 1.2 Hz,
compound was prepared from B2(OH)4 (1.12 g, 12.5 mmol), 2H), 6.93 (dd, J = 7.5, 1.0 Hz, 2H), 5.12 (s, 4H); 13C{1H} NMR (126
CH(OMe)3 (5.47 mL, 50 mmol), AcCl (9 μL, 0.125 mmol), and 1,3- MHz, CDCl3):25 δ 147.9, 128.9, 125.0, 123.6, 122.8, 118.2, 62.1; 11B
butanediol (2.27 mL, 25 mmol) according to the general procedure. NMR (160 MHz, CDCl3):25 δ 28.35. GC-MS (EI) m/z calcd for
DCM/water extraction was performed to obtain a pure compound. C14H12B2O4 [M]+ 266.09, found: 266.05.
This procedure afforded 2.0 g (81%) of the title compound as a 4.2.15. 1,1′,3,3′-Tetrahydro-2,2′-bibenzo[d][1,3,2]diazaborole
viscous oil. 1H NMR spectrum is inconsistent with the literature due (16). The title compound was prepared from B2(OH)4 (0.56 g,
to different field strengths but our 1H, 13C, and 11B are self- 6.25 mmol), CH(OMe)3 (2.73 mL, 25 mmol), AcCl (4.5 μL, 0.0625
consistent.25 1H NMR (500 MHz, CDCl3):25 δ 4.13−4.06 (m, 2H), mmol), and 1,2-diaminobenzene (1.35 g, 12.5 mmol) according to
4.02−3.98 (m, 2H), 3.95−3.90 (m, 2H), 1.94−1.88 (m, 2H), 1.73− the general procedure. The crude product was dissolved into hot dry
tetrahydrofuran (THF), filtered through a frit funnel, and transferred
1.66 (m, 2H), 1.28 (d, J = 6.3 Hz, 6H); 13C{1H} NMR (126 MHz,
into a Schlenk tube, and the solvent was removed by vacuum.
CDCl3):25 δ 66.8, 60.6, 60.5, 34.3, 34.3, 22.9, 22.9; 11B NMR (160
Redissolution in the THF followed by solvent diffusion of hexane
MHz, CDCl3):25 δ 28.04. GC-MS (EI) m/z calcd for C8H16B2O4
from an overlayer at room temperature afforded 0.92 g (63%) of the
[M]+ 198.1, found: 198.1.
title compound as an off-white solid that matched previously reported
4.2.10. 5,5,5′,5′-Tetramethyl-2,2′-bi(1,3,2-dioxaborinane) (11). spectra.31 (mp = 316-319 °C) 1H NMR (500 MHz, (CD3)SO):31 δ
The title compound was prepared from B2(OH)4 (1.12 g, 12.5 8.77 (s, 4H), 7.12−7.09 (m, 4H), 6.83−6.79 (m, 4H); 13C{1H} NMR
mmol), CH(OMe)3 (5.47 mL, 50 mmol), AcCl (9 μL, 0.125 mmol), (126 MHz, (CD3)SO):31 δ 137.3, 118.1, 110.8; 11B NMR (160 MHz,
and neopentyl glycol (2.6 g, 25 mmol) according to the general dmf-d7):31 δ 27.75. GC-MS (EI) m/z calcd for C12H12B2N4 [M]+
procedure. DCM/water extraction was performed to obtain a pure 234.1, found: 234.1.
compound. This procedure afforded 2.4 g (85%) of the title 4.2.16. Procedure for Mixture of B2pg2 with NMR Shift Reagents.
compound as a white solid that matched previously reported (a) In an oven-dried NMR tube, a mixture of NMR shift reagent
spectra.27 mp = 184−186 °C (lit mp = 182.5−184.5)28 1H NMR Eu(fod)3 (11.2 mg, 0.01 mmol) and B2pg2 (11.9 mg, 0.07 mmol) was
(500 MHz, CDCl3):27 δ 3.59 (s, 8H), 0.94 (s, 12H); 13C{1H} NMR made in 1 mL of CDCl3. (b) In an oven-dried NMR tube, a mixture
(126 MHz, CDCl3):27 δ 71.6, 31.8, 22.2; 11B NMR (160 MHz, of optical active NMR chiral shift reagent Eu(hfc)3 (11.9 mg, 0.01
CDCl3):27 δ 27.76. GC-MS (EI) m/z calcd for C10H20B2O4 [M]+ mmol) and B2pg2 (11.9 mg, 0.07 mmol) was made in 0.7 mL of
226.15, found: 226.1. CDCl3. The associated spectra were then acquired on a Varian 500
4.2.11. 4,4,4′,4′,6,6′-Hexamethyl-2,2′-bi(1,3,2-dioxaborinane) MHz DD2 NMR Spectrometer.
(12). The title compound was prepared from B2(OH)4 (1.12 g,
12.5 mmol), CH(OMe)3 (5.47 mL, 50 mmol), AcCl (9 μL, 0.125
mmol), and hexylene glycol (3.21 mL, 25 mmol) according to the
general procedure. This procedure afforded 3.0 g (97%) of the title
■ ASSOCIATED CONTENT
Data Availability Statement
compound as a white solid that matched previously reported The data underlying this study are available in the published
spectra.27 mp = 102−104 °C (lit mp = 99−101 °C)28 1H NMR article and its Supporting Information.
(500 MHz, CDCl3):27 δ 4.21−4.10 (m, 2H), 1.75−1.71 (dt, J = 13.8,
2.8 Hz, 2H), 1.50 (dd, J = 11.6, 2.0 Hz, 2H), 1.28 (d, J = 4.2 Hz, *
sı Supporting Information

12H), 1.24 (dd, J = 6.2, 1.2 Hz, 6H); 13C{1H} NMR (126 MHz, The Supporting Information is available free of charge at
CDCl3):27 δ 70.2, 70.1, 64.1, 64.1, 46.3, 46.3, 31.3, 31.2, 28.5, 28.4, https://pubs.acs.org/doi/10.1021/acs.joc.3c02992.
23.3, 23.2; 11B NMR (160 MHz, CDCl3):27 δ 28.01. GC-MS (EI) m/
Experimental details and compound characterization
z calcd for C12H24B2O4 [M]+ 254.19, found: 254.15.
4.2.12. 4,4,4′,4′-Tetramethyl-2,2′-bi(1,3,2-dioxaborinane) (13). data (PDF)
The title compound was prepared from B2(OH)4 (2.24 g, 25.0
mmol), CH(OMe)3 (10.94 mL, 100 mmol), AcCl (18 μL, 0.25
mmol), and 3-methylbutane-1,3-diol (9.15 mL, 50 mmol) according
to the general procedure. This procedure afforded 5.04 g (96%) of the
■ AUTHOR INFORMATION
Corresponding Authors
title compound as a white solid that matched previously reported Robert E. Maleczka, Jr. − Department of Chemistry, Michigan
spectra.25 mp = 62−64 °C 1H NMR (500 MHz, CDCl3):25 δ 3.99 (m, State University, East Lansing, Michigan 48824, United
4H), 1.78 (m, 4H), 1.31 (s, 12H); 13C{1H} NMR (126 MHz, States; orcid.org/0000-0002-1119-5160;
CDCl3):25 δ 69.6, 58.7, 38.5, 29.5; 11B NMR (160 MHz, CDCl3):25 δ Email: [email protected]
28.01. GC-MS (EI) m/z calcd for C10H20B2O4 [M]+ 226.15, found: Milton R. Smith, III − Department of Chemistry, Michigan
226.15. State University, East Lansing, Michigan 48824, United
4.2.13. 2,2′-Bibenzo[d][1,3,2]dioxaborole (14). The title com- States; orcid.org/0000-0002-8036-4503;
pound was prepared from B2(OH)4 (1, 1.12 g, 12.5 mmol),
CH(OMe)3 (5.47 mL, 50 mmol), AcCl (9 μL, 0.125 mmol), and
Email: [email protected]
catechol (2.75 g, 25 mmol) according to the general procedure. This Authors
procedure afforded 2.85g (96%) of the title compound as an off-white
solid that matched previously reported spectra.29 mp = 192−195 °C Ryan M. Fornwald − Department of Chemistry, Michigan
(lit mp = 195−198 °C)30 1H NMR (500 MHz, CDCl3):29 δ 7.41− State University, East Lansing, Michigan 48824, United
7.37 (m, 4H), 7.21−7.17 (m, 4H); 13C{1H} NMR (126 MHz, States
CDCl3):29 δ 147.8, 123.6, 113.2; 11B NMR (160 MHz, CDCl3):29 δ Anshu Yadav − Department of Chemistry, Michigan State
30.76. GC-MS (EI) m/z calcd for C12H8B2O4 [M]+ 238.06, found: University, East Lansing, Michigan 48824, United States;
238.06. orcid.org/0000-0001-7233-2280
6051 https://doi.org/10.1021/acs.joc.3c02992
J. Org. Chem. 2024, 89, 6048−6052
The Journal of Organic Chemistry pubs.acs.org/joc Article

Jose R. Montero Bastidas − Department of Chemistry, (15) Unsworth, P. J.; Leonori, D.; Aggarwal, V. K. Stereocontrolled
Michigan State University, East Lansing, Michigan 48824, Synthesis of 1,5-Stereogenic Centers through Three-Carbon Homo-
United States; orcid.org/0000-0002-6325-8565 logation of Boronic Esters. Angew. Chem., Int. Ed. Engl. 2014, 53 (37),
9846−9850.
Complete contact information is available at: (16) Chattopadhyay, B.; Dannatt, J. E.; Andujar-De Sanctis, I. L.;
https://pubs.acs.org/10.1021/acs.joc.3c02992 Gore, K. A.; Maleczka, R. E., Jr; Singleton, D. A.; Smith, M. R., III Ir-
Catalyzed Ortho-Borylation of Phenols Directed by Substrate−ligand
Author Contributions Electrostatic Interactions: A Combined Experimental/in Silico
† Strategy for Optimizing Weak Interactions. J. Am. Chem. Soc. 2017,
R.M.F. and A.Y. contributed equally to this work.
139 (23), 7864−7871.
Notes (17) Chen, D.; Xu, G.; Zhou, Q.; Chung, L. W.; Tang, W. Practical
The authors declare the following competing financial and Asymmetric Reductive Coupling of Isoquinolines Templated by
interest(s): M.R.S. and R.E.M. own a percentage of Chiral Diborons. J. Am. Chem. Soc. 2017, 139 (29), 9767−9770.
BoroPharm, Inc. (18) Bisht, R.; Chaturvedi, J.; Pandey, G.; Chattopadhyay, B.
Double-Fold Ortho and Remote C−H Bond Activation/Borylation of
■ ACKNOWLEDGMENTS
We thank Drs. Daniel Holmes and Li Xie of the MSU Max. T.
BINOL: A Unified Strategy for Arylation of BINOL. Org. Lett. 2019,
21 (16), 6476−6480.
(19) Yuan, J.; Jain, P.; Antilla, J. C. Bi(cyclopentyl)diol-Derived
Rogers NMR Facility, and Cassandra Johnny of the MSU Mass Boronates in Highly Enantioselective Chiral Phosphoric Acid-
Spectrometry and Metabolomics Core facility. We thank NIH Catalyzed Allylation, Propargylation, and Crotylation of Aldehydes.
(GM63188) for generous financial support and BoroPharm, J. Org. Chem. 2020, 85 (20), 12988−13003.
Inc. for supplying B2(OH)4. (20) Zhou, M.; Li, K.; Chen, D.; Xu, R.; Xu, G.; Tang, W.
Enantioselective Reductive Coupling of Imines Templated by Chiral
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