Catalytic hydroboration of aldehydes, ketones, alkynes and alkenes initiated by NaOH

Article abstract of DOI:10.1039/c7gc01632h

Commercially available NaOH powder is shown to be an efficient transition-metal-free initiator for the catalytic hydroboration of aldehydes, ketones, alkynes and alkenes with HBpin and 9-BBN under mild conditions. Combined experimental and theoretical stu

Full text of DOI:10.1039/c7gc01632h

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Catalytic Hydroboration of Aldehydes, Ketones, Alkynes and
Alkenes Initiated by NaOH
Yile Wu,*,a Changkai Shan,a Jianxi Ying,a Jue Su,a Jun Zhu,b Liu Leo Liu*,a and Yufen Zhao*,a,c
Received 00th January 20xx,
Accepted 00th January 20xx
Commercially available NaOH powder is shown to be an efficient transition-metal-free initiator for the catalytic
hydroboration of aldehydes, ketones, alkynes and alkenes with HBpin and 9-BBN under mild conditions. Combined
experimental and theoretical studies suggest that the catalytically active species is a boron hydride generated in situ from
the reaction mixture.
DOI: 10.1039/x0xx00000x
www.rsc.org/
group catalysts (Scheme 1, F-K) based on Al,18 P,19 Ge,20 Sn,20a
Mg,21 Ga22 and alkali metals23 as well as Lewis acid/Lewis acid-
base pairs24 has achieved tremendous success for the
Introduction
Organoboranes have become a class of versatile synthetic
intermediates for several important organic transformations
(e.g. the Suzuki–Miyaura reaction and Brown hydroboration
reaction) in both academic and industrial processes.1 In
contrast to other organometallic compounds, organoboranes
are widely available and an extensive library of structures can
be generated by the hydroboration of unsaturated
compounds, one of its most remarkable advantages.2 The
pursuit of efficient methods for direct hydroboration of
unsaturated bonds dates back to the middle of the twentieth
century when Brown et al. pioneered the hydroboration of
alkenes with sodium borohydride-aluminum chloride.3
Following this, great efforts have been placed into catalytic
hydroboration employing pinacolborane (HBpin) or
catecholborane (HBcat), which emerges as an efficient and
atom economic protocol for the preparation of numerous
organoboranes.4
hydroboration of carbonyl compounds and imines with high
efficiency and selectivity. However, the need for high catalyst
loading coupled with the presence of heavy metal impurities in
some cases leads to a high economic cost. The complicated
preparation of well-designed catalysts also hindered the
application of these reactions. In this regard, the development
of efficient and transition-metal-free processes would
significantly change synthetic strategies for the hydroboration
in a sustainable and atom-economic manner.25 Here, we
report the first easy-to-handle, convenient, and versatile
hydroboration of various aldehydes, ketones, alkynes and
alkenes with B-H compounds using commercially available
NaOH powder.
Hydroborations relying on well-defined transition metal
catalysts have flourished in particular. Numerous transition-
metal complexes (Scheme 1, A-E) involving Ru,5 Mo,6 Pd,7 Cu,8
Au,9 Ni,10 Fe,11 Ti,12 Zr,13 Mn,14 Hg,15 Cd,15 Rh16 and Ir17 have
displayed excellent catalytic activity in the hydroboration of
unsaturated bonds, resulting in the formation of various Scheme 1 Selected examples of transition metal complexes (A-
E) and main group catalysts (F-K) for hydroboration reactions.
valuable organoboranes. In addition, recent progress in main-
Results and Discussion
We reasoned that, as the typical Lewis acids, boranes could
readily form adducts with nucleophiles (Scheme 2), leading to
the weakening of B–H bonds with enhanced hydride
character,11c,24d which would thus facilitate the hydroboration
processes. Indeed, natural bond orbital (NBO) calculations at
the M06-2X/TZVP level of theory supported our hypothesis
(Scheme 2). The more negatively charged hydrogens of the B–
H bond suggested that the Lewis acid-base adducts feature a
stronger hydride character, compared to the corresponding
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boranes. Further, the coordination of Lewis bases could convenience of NMR monitoring. The control experiVmieewnAtrtisclheoOwnleinde
efficiently decrease the electron deficiency of the boron that without catalysts the reaction only DgOaIv:e10.t1r0a3c9e/Ca7mGCo0u1n6t32oHf
center, resulting in a weaker B–H bond (relative to HBpin or 9- product 2a (Table 1, entry 1). Next, some common and
borabicyclo[3.3.1]nonan (9-BBN)), supported also by the commercially available Lewis bases (ie. Et3N, tBuOK, and NaOH
smaller Wiberg bond indices (WBIs).
(pellets); Table 1, entries 2-4) were used as catalysts for the
reaction. Gratifyingly, the desired hydroboration product 2a was
t
formed in a good yield of 84% employing BuOK as the catalyst
(entry 3). Stronger Lewis bases such as alkali hydride NaH and N-
heterocyclic carbene 1,3-bis-(2,4,6-trimethylphenyl)imidazol-2-
ylidene (IMes)26 were also evaluated and both provided very high
yields of 2a (entries 5-6). Kawabata et al. discovered that powdered
alkali hydroxides showed better solubility in organic solvents, have
great specific surface area and high reactivity in alkylation
reactions.27 Illuminated by the previous reports, powdered NaOH
was investigated and a high yield of 99% was obtained (entry 7).
Even when the catalyst loading was decreased to 1 mol%, the
hydroboration product 2a was obtained in excellent yield after 15
minutes (entry 8). Encouraged by these promising results, solvents
were briefly screened and C6D6, CDCl3 and THF-d8 were found to be
suitable for the reaction (entries 8-10).
Scheme 2 NBO analysis of HBpin, 9-BBN and the ensuing
adducts. Selected NBO charges are given in atomic units. WBIs
are given in parentheses.
Table 1 Optimization of the reaction conditions.a
Table 2 Scope of hydroboration with aldehyde substrates.a
Entry
1
Cat.
-
Loading (mol%) Solvent Yield (%)b
-
C6D6
C6D6
C6D6
C6D6
C6D6
C6D6
C6D6
C6D6
CDCl3
THF-d8
<5
35
82
92
99
99
99
99
99
99
2
3
4
5
6
7
8
9
Et3N
5
5
5
5
5
5
1
1
1
tBuOK
NaOHc
NaH
IMes
NaOHd
NaOHd
NaOHd
NaOHd
10
a
Reaction conditions: benzaldehyde (1.00 mmol), HBpin (1.02
mmol), solvent (0.4 mL), room temperature. Catalyst loading
relative to benzaldehyde. Yields were determined by 1H NMR
b
a
Reaction conditions: benzaldehyde (1.00 mmol), HBpin (1.02
spectroscopy using 1,3,5-trimethoxybenzene as an internal
standard. c Pellets. d Powders.
mmol), NaOH (0.01 mmol), C6D6 (0.4 mL), room temperature, 15
b
1
minutes. Yields were determined by H NMR spectroscopy using
c
1,3,5-trimethoxybenzene as an internal standard. Reaction was
conducted for 1 hour. d 2 equiv of HBpin were employed. e Reaction
conditions: benzaldehyde (1.00 mmol), 9-BBN (0.5 M in THF, 1.10
On the basis of the calculations, we started our investigation
employing benzaldehyde (1a) and HBpin as model substrates at
room temperature. Deuterated solvents were employed for the
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mmol), NaOH (0.01 mmol), THF-d8 (0.5 mL), room temperature, 2
hours.
View Article Online
DOI: 10.1039/C7GC01632H
With the optimized reaction conditions in hand, we explored the
scope of this reaction with various aldehydes (Table 2). Both
electron-donating and electron-withdrawing (2b-k) aromatic groups
were well tolerated and gave excellent yields under standard
conditions. It is worth noting that even with a bulky substituent on
the arylaldehyde, the hydroboration can still be effectively
performed with a high yield of 98% (2h). Aliphatic aldehydes were
also tolerated and afforded the corresponding borate esters in good
yields (2l: 93%, 2m: 99%). Terephthalaldehyde (1n) and
isophthalaldehyde (1o) could also be used as suitable substrates to
give the corresponding diborate esters in a high yield of 95% (2n)
and 98% (2o), respectively. In addition to HBpin, 9-BBN and HBcat
were also compatible with this reaction, affording the desired
hydroboration products 2p-t in excellent yields. Notably, a large-
scale reaction of 1a (10 mmol) with HBpin (10.2 mmol) was
employed in a toluene solution under the optimized conditions and
delivered 2a in 94% yield (Scheme 3).
Scheme 3 Large-scale reaction of benzaldehyde with HBpin.
To expand the scope of this method, we next turned our attention
to ketone substrates. The hydroboration of acetophenone (3a) with
HBpin afforded the desired product 4a in 99% yield. Ketones
bearing methyl, methoxy, chloro, fluoro, bromo, trifluoromethyl
and ethynyl groups afforded the corresponding borate esters in
excellent yields (Table 3, 4a-h). Notably, the ketone moiety
displayed higher chemoselectivity over the chlorine (4d, 98%),
bromine (4e, 99%) and alkyne (4h, 96%). Heteroaromatic ketones,
such as furan-2-carbaldehyde, were also tolerated and the
corresponding product 4j was obtained in a high yield of 99%.
Although longer reaction times were required compared to the
standard conditions, biologically active compounds such as ibudilast
(3l)28 and spironolactone(3m)29 were investigated and gave the
corresponding borate esters in good yields (4l: 95% and 4m: 94%).
Furthermore, 9-BBN can also react with ketone substrates smoothly
at room temperature, affording the desired hydroboration products
4n and 4o in good yields. Imines, easily accessible from carbonyl
compounds and primary amines, are suitable precursors for the
preparation of secondary amines. Thus, next we examined imines
as substrates in the catalytic hydroboration reaction. Hydroboration
of N-methyl-1-phenylmethanimine (3p) with HBpin proceeded
a
Reaction conditions: ketone or imine (1.00 mmol), HBpin (1.02
mmol), NaOH (0.05 mmol), C6D6 (0.4 mL), room temperature, 15
minutes. Yields were determined by H NMR spectroscopy using
1,3,5-trimethoxybenzene as an internal standard. c Reaction was
conducted for 12 hours. Reaction was conducted for 24 hours.
Reaction conditions: ketone (1.00 mmol), 9-BBN (0.5 M in THF, 1.10
mmol), NaOH (0.05 mmol), THF-d8 (0.5 mL), room temperature, 2
hours. f Reaction was conducted at 90 oC for 6 hours.
b
1
d
e
Inspired by the above results, we then examined alkynes and
alkenes as substrates (Table 4). Note that catalyst-free
hydroboration of alkynes and alkenes with HBpin was reported
by Knochel et al,30 in which 2.0 equivalents HBpin, based on
alkynes and alkenes, was necessarily needed for good yields.
However, when the loading of HBpin was decreased to 1.4
equivalents, the hydroboration processes gave very poor yields
in the absence of NaOH (Table 4, footnotes c and d). To our
delight, the NaOH-initiated hydroboration of phenylacetylene
o
within 6 hours at 90 C to give borate ester 4p in a good yield of
91%.
Table 3 Scope of hydroboration with ketone and imine substrates.a
(5a) with HBpin at 100 °C furnished the corresponding borate
esters 6a in high yields. Both electron-donating and electron-
withdrawing aromatic groups bearing methyl, methoxy, fluoro
and chloro were well tolerated in this reaction (6a-e).
Substrates having a substituted group such as fluoro and
chloro on the ortho position of phenyl ring only gave moderate
to low yields (6f-g), indicating that steric hindrance affects the
reaction yields. Unfortunately, internal alkynyl such as 1,2-
diphenylethyne and methyl 3-phenylpropiolate only gave a
trace amount of the desired hydroboration products. 2-
Ethynylthiophene was also found to be suitable reaction
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50% probability level. The hydrogen atoms except those on the B
partners (6h). In addition, it is noticeable that this procotol
could be employed in the hydroboration of alkenes (5i-m)
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DOI: 10.1039/C7GC01632H
atom have been omitted for clarity.
without damaging the methoxy, fluoro, chloro, bromo
functionalities, providing the ensuing alkyl-substituted
To gain insight into the mechanism, we employed
a
stoichiometric reaction of HBpin with NaOH in THF at room
temperature. White precipitates were obtained immediately
after a THF solution of HBpin was added dropwise. The white
precipitates were filtrated and collected, but showed very
poor solubility in all usual organic solvents. Note that the
group of Clark showed the formation of a complex mixture
dioxaborolanes (6i-m) in good to moderate yields.
Table 4. Scope of hydroboration with alkyne and alkene substrates.a
containing boron-bound hydrides by treatment of
a
t
stoichiometric equivalent of BuONa with HBpin.23b It is highly
possible that any of the borohydride derivatives serve as the
active hydride source in the reaction mixture. In contrast,
treatment of 9-BBN dimer with NaOH in a molar ratio of 1:1
immediately led to a clear colorless solution (Fig. 1a). The in
situ 11B NMR spectrum revealed a clean transformation with a
broad peak at 55.98 ppm assigned to 7b31 and a triplet
resonance at –17.65 ppm (J = 74.1 Hz), which collapses into a
singlet upon proton decoupling, indicating the presence of a
BH2 fragment. Adding 15-crown-5 into the reaction mixture
allowed the formation of colorless needle crystals of 7a. X-ray
diffraction analysis confirmed the boron hydride structure of
7a with an anionic tetracoordinate boron center (Fig. 1b).32 We
found that 7a could efficiently catalyze the hydroboration of
1a with 9-BBN (Scheme 4), prompting us to consider that 7a is
likely the catalytically active species.
Scheme 4 7a-catalyzed hydroboration of 1a with 9-BBN.
a
Reaction conditions: alkyne or alkene (1.00 mmol), HBpin
(1.40 mmol), NaOH (0.08 mmol), C6D6 (0.4 mL), 100 oC, 6 hours.
b Yields were determined by 1H NMR spectroscopy using 1,3,5-
trimethoxybenzene as an internal standard. Yields in
parentheses are isolated yields after column chromatography
c
on silica. Reaction conditions: 5a (1.00 mmol), HBpin (1.40
mmol), C6D6 (0.4 mL), 100 oC, 6 hours. d Reaction conditions: 5i
(1.00 mmol), HBpin (1.40 mmol), C6D6 (0.4 mL), 100 oC, 6 hours.
Fig. 2. Proposed mechanism. Free energies are given in kcal mol-1
employing 9-BBN as the substrate.
On the basis of above analysis, a plausible reaction mechanism of
hydroboration of carbonyl compounds with 9-BBN was proposed
and supported by density functional theory (DFT) calculations at the
SMD-M06-2X/6-311++G(2d,p)//M06-2X/6-31G(d) level of theory
(Fig. 2).33 As the initial step, the generation of boron hydride IN1 is
not energy-demanding (activation barrier of 14.2 kcal mol-1) and
highly exothermic (-18.6 kcal mol-1), which could be mainly
attributed to the formation of the strong B–O bond. The approach
of 1a toward IN1 results in the formation of an intermediate IN2 (-
28.8 kcal mol-1) featuring the Na+–π interaction.34 Subsequently, the
hydridic B–H bond in IN1 would allow insertion of 1a via a four-
Fig. 1 (a) The reaction of 9-BBN with NaOH. (b) Molecular structure
of 7a with the anisotropic displacement parameters depicted at the
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Fernández, Chem. Soc. Rev. 2017, 46, 415-430. (h) J. W. B.
membered ring transition state TS2 (-6.8 kcal/mol) with an
activation barrier of 28.8 kcal mol-1 (IN1→TS2). Finally, the
hydroboration product extrusion (-70.0 kcal mol-1) with the aid of a
9-BBN completes the catalytic cycle to regenerate the catalytically
active species IN1. We note that the results and the interpretations
presented here might be insufficient to support the generation of
H2Bpin anion from the reaction of HBpin and NaOH. Another
possible mechanism consists of coordination of NaOH to boron as
the reactive species cannot be ruled out.
View Article Online
Fyfe and A. J. B. Watson, Chem, 2017, DOI: 10.1039/C7GC01632H
3, 31-55.
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(a) G. C. Fu, in Transition Metals for Organic Synthesis, Wiley-
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Conclusion
In conclusion, we have developed a general and efficient catalytic
hydroboration of aldehydes, ketones, alkynes and alkenes using
powdered NaOH as the initiator. Utilizing this low toxic,
commercially available, cheap, and stable powder as the initiator
instead of environmentally unfriendly transition metals is extremely
attractive. Coupled with its remarkable substrate tolerance, high
chemo-selectivity, and good yields mean that this method will be
appealing for organic synthesis. In contrast to the observations that
the proposed active hydride source could not be isolated in the
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boron hydride 7a. Preliminary mechanistic study revealed that 7a is
the catalytically active specie generated in situ in the reaction,
which also paves a new way to produce the anionic H2BR2 species.
Further studies of this newly discovered catalytic system are the
subject of on-going investigation.
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Conflicts of interest
There are no conflicts of interest to declare.
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Acknowledgements
This work was supported by the National Natural Science
Foundation of China (No. 21375113 and 21573179) and the
National Basic Research Program of China (No. 2012CB821600 and
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