Base-catalysed reductive relay hydroboration of allylic alcohols with pinacolborane to form alkylboronic esters

Article abstract of DOI:10.1039/c9cc03459e

An unprecedented base-catalysed reductive relay hydroboration of allylic alcohols is described. Commercially available ⁿBuLi was found to be a robust transition metal-free initiator for this protocol, affording various boronic esters in high yield and selectivity. Mechanistically, this methodology involves a one-pot three-step successive process (dehydrocoupling/allylic hydride substitution/anti-Markovnikov hydroboration).

Full text of DOI:10.1039/c9cc03459e

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DOI: 10.1039/C9CC03459E
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Base-Catalysed Reductive Relay Hydroboration of Allylic Alcohols
with Pinacolborane to Form Alkylboronic Esters
Zi-Chao Wang,a,b Di Shen,a,b Jian Gao,a,b Xian Jia,a Youjun Xu,*,a and Shi-Liang Shi*,b
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
An unprecedented base-catalysed reductive relay hydroboration of
allylic alcohols is described. Commercially available nBuLi was
found to be a robust transition-metal-free initiator for this protocol,
affording various boronic esters in high yield and selectivity.
Mechanistically, this methodology involves a one-pot three-step
successive process (dehydrocoupling / allylic hydride substitution/
anti-Markovnikov hydroboration).
R2
R2
base (cat.)
R1
Bpin
R1
OH
HBpin
reductive relay hydroboration
R2
R2
R1
OBpin
Organoboronic esters are an important class of synthetic
intermediates, which are commonly used in the field of total
synthesis, drug development and materials science.1
Organoboronic esters are attractive because of their easy
availability, appropriate reactivity and stability, and low toxicity.
The versatile C-B bonds can be transformed into a wide variety
of products, including those bearing C-C, C-N, C-O, and C-X (X =
halide) bonds.2 Accordingly, numerous well-defined transition-
metal complexes have been developed to enable highly
selective hydroboration reactions of unsaturated hydrocarbons
to form alkylboronic esters.3,4 In addition, main group metals5,
and metal-free catalysis6,7 have recently been reported to
promote hydroboration of unsaturated bonds. However, in
contrast, simple base-catalysed hydroboration of alkenes and
alkynes8 has been less investigated,9 despite that it serves as a
sustainable and easy to handle hydroboration method as no
need of complicated preparation of ligands and catalysts.
On the other hand, metal-catalysed tandem alkene
isomerization/hydroboration reactions10,11 and cascade
borylative reactions12 have recently been advanced to afford
borylated products otherwise synthesized in multi-step
R1
Scheme 1. Base-catalysed reductive relay hydroboration of
allylic alcohols (this work)
reactions. Such cascade reactions are highly desirable, as
potentially tedious workup and purification steps can be
avoided.13 However, to our knowledge, a base-catalysed alkene
isomerization and hydroboration sequential reaction remains
unknown. We became interested in developing base-catalysed
reductive relay hydroboration of allylic alcohols as a convenient
approach to access alkylboronic esters (Scheme 1). In particular,
we envisioned that
a suitable base would promote a
dehydrocoupling of allylic alcohols and pinacolborane,14 and
further promote a subsequent allylic hydride substitution to
form a transient terminal alkene, which would then undergo
hydroboration again to afford the alkylboronic ester products.
If successful, this approach would be particularly attractive due
to not only the abundance of a base catalyst but also the easy
accessibility of starting materials15 relative to the preparation of
a specific terminal alkene bearing α-substitutions or toxic alkyl
halides for borylation reactions16. We noted that, although the
metal-catalysed allylic substitution with hydride nucleophiles is
known,17 the proposed base-catalysed allylic hydride
substitution is an unprecedented process.18 Moreover, base-
catalysed hydroboration of α-alkene remain unexplored.8 In
addition, the control of regioselectivities in these multi-
a.
School of Pharmaceutical Engineering, and Key Laboratory of Structure-Based
Drug Design & Discovery (Ministry of Education), Shenyang Pharmaceutical
University, Shenyang 110016, China.
E-mail: xuyoujun@syphu.edu.cn
State Key Laboratory of Organometallic Chemistry, Center for Excellence in
b.
hydroboration processes is non-trivial.3 Herein, as
continuation of our works on alkene hydroboration,19 we report
a base-catalysed reductive relay hydroboration of allylic
a
Molecular Synthesis, Shanghai Institute of Organic Chemistry, Chinese
Academy of Sciences, 345 Lingling Road, Shanghai 200032, China
E-mail: shiliangshi@sioc.ac.cn
Electronic
Supplementary
Information
(ESI)
available:
See
DOI: 10.1039/x0xx00000x
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J. Name., 2013, 00, 1-3 | 1
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Table 2. Substrate scopea
alcohols and derivatives with pinacolborane to prepare a wide
variety of alkylboronic esters in one chemical step.
View Article Online
DOI: 10.1039/C9CC03459E
R2
R2
nBuLi (10 mol%)
toluene (1.0 M)
130 oC, 12 h
HBpin
R1
OH
(0.5 mmol)
R1
Bpin
We started our investigation by examining hydroboration of
3-phenylbut-2-en-1-ol (1a, E/Z: 6/1) with HBpin to form
alkylboronic ester 3a in the presence of 10 mol% of various base
catalysts (Table 1). At the outset, the control reaction between
1a and HBpin was conducted at 100 oC in the absence of base,
product 3a formed in trace amount (entry 1). We reasoned that
bases or nucleophiles could easily form adducts with Lewis
acidic boranes (HBpin) to activate the B-H bonds with a more
hydridic character,20 which thus facilitate the hydroboration
1
3.5 equiv
Me
3-4
Me
Me Me
Me
O
O
Bpin
Bpin
Bpin
Bpin
Bpin
R
Me
3i
3
3k
, 90%
j, 99%
, 91%
Me
3a
R = H, , 92%
3b
R = Ph, , 97%
3c
R = morpholinyl, , 88%
Me
Me
3d
R = OCF3, , 88%
3e
R = CF3, , 96%
O
S
Bpin
Bpin
3f
R = SCH3, , 93%
MeO
N
3g
R = Br, , 85%
3l
3m
3n
, 83%
,
86%
nPr
, 92%
Bn
3h
R = Cl, , 91%
t
processes. Indeed, the use of base catalysts, including BuOK,
Me
Me
Me
S
tBuONa, and tBuOLi, all promoted the hydroboration reactions,
affording 52-69% yields of 3a (entries 2-4). Surprisingly, the use
of weak bases (KOAc and K3PO4) as an initiator for the
hydroboration would deliver moderate yields of 3a, while the
reactions using KOH and CsF gave lower yields (entries 5-8). We
rationalized that the potential bidentate coordination of
acetate and phosphate anion to boron center might accelerate
the hydroboration. We were pleased to find that nBuLi was the
best catalyst for this cascade transformation, providing 3a in 83%
yield (entry 9). Finally, increasing the reaction temperature to
130 oC further improved the yield to 96% (entry 10). Importantly,
all these reactions proceeded in excellent regioselectivity,
delivering linear alkylboronic esters as a single isomer.
Bpin
Bpin
N
Bpin
Bpin
S
Me
3o
3p
3q
3r
, 87%
, 73%
, 83%
, 97%
Bpin
H
Bpin
R
Bpin
H
Bpin
b
H
3u
R = H, , 57%
b
H
3v
R = 4-NMe2, , 67%
b
3s
3t
3x
, 82%
, 70%
, 93%
3w
R = 2-OMe,
, 72%
Ph
Me
Me
Me
nPent
Bpin
Bpin
Ph
Bpin Me
Bpin Ph
, 78%
Bpin
Ph
c
3y
3z
4a
4b
4c
, 78%
, 93%
, 99%
Me
, 86%
Me
Me
Me
Me
Me
Me
Me
Me
OH
Me
Bpin
geraniol
nerol
Table 1. Reaction optimization
OH
4d
Me
H
Me
Me
from geraniol, 79%
from nerol, 64%
Me
base (10 mol%)
toluene (1.0 M)
100 oC, 12 h
Me
Me
Me
O
Me
R
5
from , 55%
HBpin
Me
6
from , 64%
Ph
Bpin
5, R=OAc
, R=OTBS
Ph
1a
OH
(0.2 mmol)
Ph
7
7
from , 84%
6
Bpin
2
(0.7 mmol)
3a/3a'
>99/1
3a
3a'
aIsolated yields are given; Unless otherwise indicated, single
regioisomer (>99/1) of hydroborated products were obtained. b24 h.
cLinear/branched ratio is 94:6.
Base
/
Yield (%)a
Entry
Base
Yield (%)a
Entry
1
2
3
4
5
<5
57
52
69
61
52
40
9
K3PO4
CsF
6
7
tBuOK
tBuONa
tBuOLi
KOAc
group (3d), amines (3c, 3v) and trisubstituted alkenes (4d). Most
remarkably, substrates possessing aryl bromide (3g), aryl
chloride (3h), furan (3l), thiophene (3m), benzothiophene (3o),
pyridine and thiazole (3n, 3p), functional groups which are
reactive to nBuLi through lithium-halogen exchange or
deprotonation even at low temperature, participated in this
reaction smoothly affording high yields of products. These
results indicated that the reaction conditions be considerably
KOH
nBuLi
nBuLi
8
83
96
9
10b
a
Yields were determined by NMR analysis using 1,3,5-trimethyl-
benzene as an internal standard; the 3a/3a’ ratios were
determined by GC-MS analysis of the crude reaction mixture.
bRun at 130 oC.
n
mild as BuLi was quenched through the formation of borane
adducts with HBpin. To further examine the functional group
compatibility of this protocol, an additive-based robustness
screen was conducted.21,22 The screen suggested the tolerance
of the reaction to benzylic alcohols, acetals, secondary amines,
morpholine, indoles, pyrroles, carbazoles, and benzothiadiazole.
Ester, amide, and nitrile functional groups were likely reduced
to alcohol and amines respectively under the reaction
conditions although the product 3a was obtained in high yields.
The use of geraniol and nerol both gave good yields of
alkylboronic ester product 4d. Substrates with acetate (5) and
silyl ether (6) leaving group also provided products in
synthetically useful yields. Interestingly, the use of an enal 7
underwent a selective 1,2-reduction followed by the reductive
relay hydroboration process to form 4d in high yield. It is
noteworthy that in all these cases trisubstituted alkene moieties
were kept intact under these conditions.
With the optimized conditions in hand, we next investigated
the scope of this novel reductive hydroboration protocol. As
shown in Table 2, a diverse array of alkylboronic esters were
prepared in high to excellent yields from a series of allylic
alcohols substrates, including those bearing 3,3-alkyl, aryl
substituents (3a-3t), 3,3-dialkyl substituents (3z, 4a, 4d), 3,3-
diaryl substituents (3y), monoaryl (3u-3w) and monoalkyl
substituents (4b, 4c). In addition to acyclic substrates, the use
of cyclic allylic alcohols also gave hydroborylated products in
high yields (3s, 3t, 3x). The steric and electronic effects of aryl
substituents were not sensitive to this cascade reaction.
Moreover, substrates with many functional groups are
compatible in this reaction, including ethers (3k, 3n, 3w), a
thioether (3f), a trifluoromethyl group (3e), a trifluoromethoxyl
2 | J. Name., 2012, 00, 1-3
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Next, a gram-scale reaction (5 mmol scale) using 1a was reaction of 1a with HBpin at the room temperature in the
View Article Online
n
successfully performed to deliver alkylboronic ester 3a in near presence of 10 mol% BuLi gave a nearlDyOqI:u1a0n.1t0it3a9t/Civ9eCCyi0e3l4d59oEf
quantitative yield, highlighting the practicality of the dehydrocoupling product (13) as determined by 1H and 11B NMR
hydroboration method (Scheme 2). To further demonstrate the analysis (eqn 1). Increasing the temperature to 130 oC
synthetic utility of our hydroboration method, we converted C- converted 13 to product 3a in high yield (eqn 1). Besides, the
B bonds in 3a into various important classes of carbon-carbon formation of (pinB)2O was observed by 11B NMR analysis. Then,
and carbon-heteroatom bonds.23 For example, 3a smoothly we found that alkene 14 undergo the hydroboration in similarly
underwent vinylation and arylation to produce 823a and 94d in high efficiency under the standard reaction conditions,
good efficiency, respectively. In addition, the subjection of 3a to indicating 14 could be the real hydroboration precursor to form
a typical oxidation condition and oxidative amination condition product 3a (eqn 2). As expected, no hydroboration reaction of
n
readily afforded an alcohol 10 and an amine 11,23b respectively. 14 occurred in the absence of BuLi. Additionally, when the
Finally, simple bromination condition furnished alkyl bromide model reaction was run using 2.0 equiv HBpin under the
12 in 77% yield.23c Given the easy availability of substrates and standard conditions, we observed the formation of 13 and
rich chemistry of organoboron compounds, the current product 3a, but without the detection of alkene 14, which
reductive hydroboration protocol would provide a convenient suggests the hydroboration of transient terminal alkene might
and powerful mean of the transformation of allylic alcohols.
be fast and not the rate-limiting step. Finally, the use of methyl
ether of 1a (15) also gave 3a in a nearly quantitative yield (eqn
4). On the basis of these results, we proposed a plausible
catalytic cycle for this reaction. As shown in Figure 1, a
dehydrocoupling of allylic alcohol and HBpin give 13.14 Further
base-promoted regioselective hydroboration of 13 and
subsequent -oxygen elimination (path a) or an SN2’ allylic
hydride substitution (path b) produces alkene 14, which
Me
5 mmol scale
Ph
OH
1a
a
99%
Ph
Ph
Br
b
Me
f
Me
8
63%
77%
Ph
Bpin
12
undergoes
exclusive
anti-Markovnikov
hydroboration
Me
3a
92%
furnishing the linear alkylboronic ester product 3a.
c
e
70%
Me
N
52%
Me
Me
d
Ph
Ph
Ph
Ph
Base
Ph
OH
Ph
Bpin
Me
1a
Me
9
3a
11
Me
Ph
OH
10
H2
Me
Ph
Me
HBpin
a1a
1c
(5.0 mmol, 1.3 g), nBuLi (10 mol %), HBpin (3.5 equiv), toluene (5.0 mL), 130 oC, 12 h. b1)
Bpin
3a'
(0.2 mmol), vinylmagnesium bromide (4.0 equiv), THF (3.0 mL), -78 oC, 30 min. 2) I2 (4.0 equiv)
HBpin
Base
c1c
in MeOH, r.t., 30 min.
BINAP (0.12 equiv), NaOH (15.0 equiv), THF: H2O (5:1, 1.2 mL), 100 oC, 16 h.
NaBO3 H2O (3.0 equiv), THF: H2O (1:1, 2. mL), r.t., 6 h.
equiv), tBuOOtBu (2 equiv), Cu(OAc)2 (5 mol%), toluene (2.0 mL), 80 oC, 24 h. f1)
(0.2 mmol), bromobenzene (1.5 equiv), Pd(OAc)2 (10 mol %), rac-
d1c
(0.2 mmol),
Me
Reductive Relay
Hydroboration
Me
e1c
(0.2 mmol), N-methylaniline (1.5
Ph
OBpin
1c
(0.2 mmol),
Ph
13
Base
HBpin
phenyllithium (2.0 equiv), THF (1.0 mL), r.t., 30 min. 2) NBS (2.0 equiv), THF (1.0 mL), r.t., 1 h.
Base = nBuLi or LiOR
Me
14
Scheme 2. Gram-scale reaction and transformation of 3a.
pinBOBpin
Ph
OBpin
Bpin
or
Base
Me
Me
nBuLi (10 mol%)
toluene (1.0 M)
25 oC, 30 min
path a
130 o
OBpin 12 h
C
HBpin
3a (eqn 1)
Base
Ph
Ph
OH
(0.5 mmol)
Me
H
Bpin
Me
1a
3.5 equiv
13,
path b
>95 %
Me
92%
Ph
OBpin
nBuLi (10 mol%)
toluene (1.0 M)
130 oC, 12 h
HBpin
(eqn 2)
(eqn 3)
Figure 1. Proposed catalytic cycle.
Ph
Ph
3a
Bpin
1.2 equiv
14,
0.5 mmol
, 95%
w/o nBuLi, <5 %
Me
In summary, we have developed an efficient and
unprecedented base-catalysed reductive relay hydroboration of
allylic alcohols with pinacolborane. Inexpensive nBuLi was used
as a simple transition-metal-free initiator for this cascade
process, converting a diverse variety of allylic alcohols and
derivatives bearing various heterocycles and functional groups
to alkylboronic esters in a single operation. A mechanism
involving a one-pot three-step sequential process was proposed.
Efforts to further development of efficient hydroboration
reactions are ongoing in our laboratory.
nBuLi (10 mol%)
toluene (1.0 M)
130 oC, 12 h
HBpin
3a
+
13
+
14
Ph
OH
(0.5 mmol)
Me
35%
65%
0%
2.0 equiv
1a
Me
nBuLi or tBuOLi (10 mol%)
toluene (1.0 M)
HBpin
(eqn 4)
Ph
15
OMe
(0.2 mmol)
Ph
Bpin
130 oC, 12 h
3.5 equiv
3a
, >95%
Scheme 3. Mechanistic experiments
To further understand the mechanism of this reaction, we
performed some additional experiments (Scheme 3). Firstly, the
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Jeong, J. Heo, S. Park and S. Chang, Chem. Eur.VieJw., A2rt0ic1le9O,n2lin5e,
We acknowledged the financial support from the Strategic
Priority Research Program of the Chinese Academy of Sciences
(XDB20000000), “1000-Youth Talents Plan”, NSF of China
(21690074, 21871288, 91856111, 21821002), “innovative
research team of the Ministry of Education” and "innovative
research team in SYPHU by the supporting fund for universities
from the Chinese Central Government (51150039)".
6320.
DOI: 10.1039/C9CC03459E
8
9
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4 | J. Name., 2012, 00, 1-3
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