Chemodivergent Synthesis of One-Carbon-Extended Alcohols via Copper-Catalyzed Hydroxymethylation of Alkynes with Formic Acid

Article abstract of DOI:10.1021/acs.orglett.1c01473

The development of selective catalytic reactions that utilize easily available reagents for the efficient synthesis of alcohols is a long-standing goal of chemical research. Here an intriguing strategy for the chemodivergent copper-catalyzed hydroxymethylation of alkynes with formic acid and hydrosilane has been developed. By simply tuning the amount of formic acid and reaction temperature, distinct one-carbon-extended primary alcohols, that is, allylic alcohols and β-branched alkyl alcohols, were produced with high levels of Z/E-, regio-, and enantioselectivity.

Full text of DOI:10.1021/acs.orglett.1c01473

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Letter
Chemodivergent Synthesis of One-Carbon-Extended Alcohols via
Copper-Catalyzed Hydroxymethylation of Alkynes with Formic Acid
Xin Jin,⊥ Hong-Chen Fu,⊥ Mei-Yan Wang,* Shouying Huang, Yue Wang, Liang-Nian He,
and Xinbin Ma*
Cite This: Org. Lett. 2021, 23, 4997−5001
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ABSTRACT: The development of selective catalytic reactions that utilize easily available reagents for the efficient synthesis of
alcohols is a long-standing goal of chemical research. Here an intriguing strategy for the chemodivergent copper-catalyzed
hydroxymethylation of alkynes with formic acid and hydrosilane has been developed. By simply tuning the amount of formic acid
and reaction temperature, distinct one-carbon-extended primary alcohols, that is, allylic alcohols and β-branched alkyl alcohols, were
produced with high levels of Z/E-, regio-, and enantioselectivity.
lcohols play a critical role in the chemical and
pharmaceutical industries. For the synthesis of one-
A
carbon-extended primary alcohols, the general strategy is the
hydroxymethylation reaction typically being achieved by the
stepwise installation and subsequent reduction of a carbonyl
moiety, such as the hydroformylation−hydrogenation of
olefins or alkyl electrophiles with CO (Figure 1a).1 Although
many transition-metal catalytic systems such as Co,2 Pd,3 Rh,4
or Ru5 have been applied to the hydroxymethylation of α-
olefins with CO/H2, the regioselectivity and chemoselectivity
have been proven to be challenging. By using paraformalde-
hyde (Figure 1b), methanol, or CO2 as sustainable C1
feedstocks, many efforts to carry out the hydroxymethylation
of unsaturated hydrocarbons, for example, 1,3-dienes,6 allenes,7
and alkynes,8 have also been made. In particular, Yu and Ding
et al. achieved the enantioselective reductive hydroxymethyla-
tion of 1,3-dienes/allenes with CO2, giving a series of chiral
homoallylic alcohols (Figure 1c).9 Despite the great advances
made in the accessibility of primary alcohols, research on
chemodivergent synthesis to produce distinct alcohols using a
single copper catalyst system remains very challenging.
Recently, we realized the chemoselective synthesis of
primary alcohols via the CuH-catalyzed hydroxymethylation
of alkynes with CO2.10 By controlling the introduction of
additional protons, such as tBuOH, allylic alcohols and
homobenzylic alcohols could be separately furnished. Because
formic acid can be obtained from CO2 hydrogenation,11 it is
normally regarded as a kind of activated CO2, and compared
with CO2, which usually needs to be introduced from cylinders
Figure 1. Selected examples of the synthesis of one-carbon-extended
alcohols.
Received: April 29, 2021
Published: June 1, 2021
https://doi.org/10.1021/acs.orglett.1c01473
© 2021 American Chemical Society
Org. Lett. 2021, 23, 4997−5001
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as a gas or through the sublimation of dry ice, formic acid is
readily available as a solution. Thus we attempted to employ
formic acid as an alternative and user-friendly hydroxymethyl
source for the hydroxymethylation of alkynes. More
importantly, as an excellent protic output buffer that gently
releases protons, the formic acid meanwhile may be a proton
source to self-regulate the chemoselectivity of alkyne
hydroxymethylation to produce distinct alcohols (Figure 1d),
thus avoiding the addition of an extra proton.
(entry 8). The effect of temperature on the divergence of
products brought great enlightenment to the subsequent
regulation of the chemoselectivity of this reaction.
With the optimized conditions in hand, we then evaluated
the scope of the direct hydroxymethylation of alkynes with
formic acid. As shown in Scheme 1, a variety of internal
Scheme 1. Direct Hydroxymethylation of Various Alkynes
with Formic Acid
We initiated our investigation for the reactivity of direct
alkyne hydroxymethylation by treating 1,2-diphenylacetylene
(1a) and formic acid (1.5 equiv to 1a) with triethoxysilane,
using Cu(OAc)2 coupled to a range of rigid biphosphine
ligands as catalysts (Table 1, entries 1−4). Although the
Table 1. Optimization of the Direct Hydroxymethylation of
a
Alkynes with Formic Acid
b
entry
ligand
temp (°C)
yield (%)
21
56
c
1
2
3
4
5
L1
L2
L3
L4
L5
L4
L4
L4
55
55
55
55
55
55
90
rt
aromatic alkynes with electron-donating and mildly electron-
withdrawing substituents all reacted smoothly to give the
corresponding trisubstituted allylic alcohols 2b−2f with
complete E-stereoselectivity. There was a slight decrease in
the reactivity of meta- or ortho-substituent diphenyl alkynes,
presumably due to the steric hindrance (2g, 2h). The
bithiophenyl alkyne was also reactive, delivering the (Z)-2,3-
di(thiophen-2-yl)prop-2-en-1-ol (2i) in 71% yield. Remark-
ably, a high regioselectivity was attained in the hydroxyme-
thylation of cyclopropylphenylethyne, affording the major
product 2j. In addition, in the investigation of scope with
respect to simple terminal alkynes, anti-Markovnikov regiose-
lectivity was observed, giving rise to linear allylic alcohols 2k
and 2l in mild yields. In addition, a satisfactory yield (65%) of
2a was obtained when the direct hydroxymethylation of 1a was
performed on a 6 mmol scale. For more information on the
optimization and large-scale experiment, see the Supporting
Information, Sections 2.1 and 2.3.
Considering that an elevated temperature favors the
protonation of the vinylcopper species to produce an alkene,
as shown in the optimized results of the direct alkyne
hydroxymethylation, we then explored the reductive hydrox-
ymethylation of 1a by increasing the temperature to 90 °C as
well as the amount of formic acid to 3 equiv. It was
disappointing that only 1,2-diphenylethene, 1,2-diphenyl-
ethane, and a trace of 2a were obtained. But when the
terminal alkyne of 4-ethynyl-1,1′-biphenyl (3a) was introduced
instead of 1a, fortunately, a 78% yield of 2-([1,1′-biphenyl]-4-
yl)propan-1-ol (4a) was generated coupled to a small amount
of 4-vinyl-1,1′-biphenyl and 4-ethanyl-1,1′-biphenyl. We
attribute the poor reactivity of 1a to the impediment of the
hydroxymethylation of its semireduction product, that is, 1,2-
d
91 (87)
51
43
38
15
e
6
7
8
a
Reactions were conducted in a 10 mL Schlenk tube. Conditions: 1a
(0.0712 g, 0.4 mmol), Cu(OAc)2 (0.0072 g, 0.040 mmol), L (0.044
mmol), CsOAc (0.0039 g, 0.02 mmol), HCOOH (0.6 mmol, 23 μL),
(EtO)3SiH (4.5 mL, 2.4 mmol), cyclohexane (2 mL), 55 °C, 24 h.
b
1
Determined by the H NMR technique using 1,1,2,2-tetrachloro-
c
d
ethane as an internal standard. Not detected. Isolated yield.
e
(EtO)3SiH (1.6 mmol).
Xantphos (L1)- and DTBM-MeO-BIPHEP (L2)-based copper
catalysts were positive toward the generation of (E)-2,3-
diphenylprop-2-en-1-ol (2a), Cu(OAc)2 combined with
DTBM-SEGPHOS (L4) was found to be the most efficient,
affording 2a as a complete E-type geometric isomer, as
1
determined by H NMR analysis (entry 4). The investigation
of the alkyl biphosphine ligand showed that (S,S)-Ph-PBE
(L5) could have a moderate effect on the generation of 2a
(entry 5). A sharp decrease in the yield of 2a was observed
when the amount of triethoxysilane was reduced (entry 6),
probably because the comparable hydrosilylation of formic
acid consumed a certain amount of hydrosilane. Further
optimization showed that an elevated temperature went against
the generation of allylic alcohols but was beneficial to the
protonation of the vinylcopper species to produce 1,2-
diphenylethene (entry 7). When the temperature was lowered
to room conditions, a poor conversion of 1a was obtained
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diphenylethene.12 Further optimization of the temperature and
ligands demonstrated that (R)-L4 performed remarkably well
in the reductive hydroxymethylation in regards to enantiose-
lectivity and reactivity at 70 °C, delivering 4a in 85% yield. The
rigid structure and steric hindrance, which are favorable to the
stereochemical stability of the benzylic copper, may account
for the excellent performance of the enantioselectivity of
copper catalyst based on (R)-L4.10,13 Details of the
optimization of the reductive hydroxymethylation are given
in the Supporting Information, Table S2.
Scheme 3. Controlled Experiments and Isotope-Labeling
Study
We subsequently evaluated the substrate scope of reductive
hydroxymethylation. Markovnikov regioselectivity and excel-
lent enantioselectivity were observed in all of the substrates
studied. As shown in Scheme 2, a range of enantioenriched β-
Scheme 2. Substrate Scope of Reductive
Hydroxymethylation
elevated temperature is beneficial to the protonation of the
vinylcopper species. The further reaction of 4-vinyl-1,1′-
biphenyl with formic acid under the standard conditions of
reductive hydroxymethylation delivered 4a in 92% yield with
97% e.e. (Scheme 3c). The previously described results suggest
that the reductive hydroxymethylation proceeds with a
temperature-directed and proton-switched cascade sequence
of alkyne semireduction to alkene followed by the hydrox-
ymethylation of the alkene to an enantiopure alcohol. In
addition, although triethoxysilyl formate could be obtained
from triethoxysilane and formic acid with copper catalysis, the
reaction of triethoxysilyl formate with 3a or 4-vinyl-1,1′-
biphenyl failed to give product 4a,10 demonstrating that silyl
formate is not an intermediate. Instead, as a competitive side
reaction, the hydrosilylation of formic acid consumes a certain
amount of hydrosilane. That is why an excess of hydrosilane is
essential to obtain a good production of alcohols.
branched alkyl alcohols (4b−4e) were attained from terminal
aromatic alkynes with electron-donating substituents at the
para position of the biphenyl backbone (61−86% yield, 73−
98% e.e.). Although the reactivity of substrates containing a
mildly electron-withdrawing group was slightly reduced, the
enantioselectivity could be well maintained (4f−4h). The
alkynes bearing a fused aromatic ring or a heteroarene such as
a thiophene ring were both well tolerated, delivering the
desired products (4i, 4j) in moderate yield. Although the
reductive hydroxymethylation of internal alkynes was not
successful, the current method represents a good example of
the highly regio- and enantioselective construction of β-
branched alkyl alcohols from terminal alkynes.
On the basis of experimental results and previous
literature,9a,c,10,13 the catalytic cycle for the copper-catalyzed
selective hydroxymethylation of alkynes with formic acid is
proposed (Scheme 4). The direct hydroxymethylation and
reductive hydroxymethylation both commence with the
Scheme 4. Proposed Mechanism
To better understand the reaction mechanism of this
copper-catalyzed selective hydroxymethylation of alkynes
with formic acid, we carried out a series of controlled
experiments focusing on the reductive hydroxymethylation.
First, the isotope-labeling study carried out in the presence of
deuterated formic acid (DCOOD, HCOOD) verifies that
formic acid serves as both a carbonyl source and a proton
source, as the incorporation of deuterium in the methyl moiety
1
of 4a′ was observed by H NMR (Figures S1−S3) (Scheme
3a). The semireduction of 3a with 1 equiv of formic acid at
both 70 and 50 °C was then separately explored. A 78% yield
of 4-vinyl-1,1′-biphenyl was produced at 70 °C, much higher
than that at 50 °C (19%) (Scheme 3b), confirming that an
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Letter
hydrocupration of CuH to the alkyne substrate to give the
vinylcopper intermediate I. At low temperature and low
concentration of formic acid, the direct carbonylation of I
delivers the copper carboxylate II. The intermediate II is
further reduced to an alkoxylcopper intermediate III that
regenerates the CuH species upon transmetalation with
hydrosilane. On the contrary, with an increase in temperature
and an increase in the amount of formic acid, prior to being
intercepted by the proton released from the formic acid, the
vinylcopper forms a transient alkene. Subsequently, a similar
hydrocupration occurs in the alkene to produce a stereodefined
alkylcopper species V, which then reacts with formic acid to
give alkoxycopper species VI. Further reduction of VI by
hydrosilane furnishes the product of alkyl alcohols.
In summary, an attractive method for the copper-catalyzed
chemoselective hydroxymethylation of alkynes with formic
acid was developed. In this protocol, by simply tuning the
amount of formic acid and the reaction temperature, direct
hydroxymethylation and reductive hydroxymethylation could
be triggered, respectively. Such a chemoselective synthesis is
attributed to the different responses of vinyl- and alkylcopper
intermediates to the proton and carbonyl of formic acid. That
is, with a lower amount of formic acid (1.5 equiv of the alkyne
substrate) at 55 °C, the vinylcopper intermediate first reacts
with the carbonyl of formic acid, generating the direct
hydroxymethylation products of allylic alcohols with high
chemo- and Z/E-selectivity. On the contrary, an elevated
temperature (70 °C) and excessive formic acid (3 equiv) are
beneficial to the protonation of the vinylcopper species
followed by the oriented carbonylation of the alkylcopper
intermediate. Thus the reductive hydroxymethylation is
facilitated, outputting a series of β-branched alkyl alcohols
with high levels of regio- and enantioselectivity.
Tianjin 300072, China; orcid.org/0000-0002-2210-
0518; Email: xbma@tju.edu.cn
Authors
Xin Jin − Key Laboratory for Green Chemical Technology of
Ministry of Education, School of Chemical Engineering and
Technology, Tianjin University, Tianjin 300072, China
Hong-Chen Fu − State Key Laboratory and Institute of
Elemento-Organic Chemistry, Nankai University, Tianjin
300071, China
Shouying Huang − Key Laboratory for Green Chemical
Technology of Ministry of Education, School of Chemical
Engineering and Technology, Tianjin University, Tianjin
300072, China; orcid.org/0000-0002-8376-2638
Yue Wang − Key Laboratory for Green Chemical Technology
of Ministry of Education, School of Chemical Engineering and
Technology, Tianjin University, Tianjin 300072, China;
orcid.org/0000-0002-2362-3345
Liang-Nian He − Collaborative Innovation Centre of
Chemical Science and Engineering, Tianjin University,
Tianjin 300072, China; State Key Laboratory and Institute
of Elemento-Organic Chemistry, Nankai University, Tianjin
300071, China; orcid.org/0000-0002-6067-5937
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.orglett.1c01473
Author Contributions
⊥X.J. and H.-C.F. contributed equally.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This work was supported by the National Natural Science
Foundation of China (21808164), National Key R&D
Program of China (2018YFB0605801), and China Postdoc-
toral Science Foundation (2018M631744, 2020T130466).
ASSOCIATED CONTENT
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AUTHOR INFORMATION
■
Corresponding Authors
Mei-Yan Wang − Key Laboratory for Green Chemical
Technology of Ministry of Education, School of Chemical
Engineering and Technology, Tianjin University, Tianjin
300072, China; Joint School of National University of
Singapore and Tianjin University, International Campus of
Tianjin University, Fuzhou 350207, China; Collaborative
Innovation Centre of Chemical Science and Engineering,
Tianjin University, Tianjin 300072, China; orcid.org/
0000-0002-2642-8166; Email: mywang2017@tju.edu.cn
Xinbin Ma − Key Laboratory for Green Chemical Technology
of Ministry of Education, School of Chemical Engineering and
Technology, Tianjin University, Tianjin 300072, China; Joint
School of National University of Singapore and Tianjin
University, International Campus of Tianjin University,
Fuzhou 350207, China; Collaborative Innovation Centre of
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