One-pot transformation of alkynes into alcohols and amines with formic acid

Article abstract of DOI:10.1039/c3gc41133h

Alkynes are converted into alcohols and amines through a formic acid-participated alkyne-to-ketone transformation and transfer hydrogenation process. The reaction proceeds well under aqueous conditions, furnishing chiral alcohols directly from alkynes for the first time.

Full text of DOI:10.1039/c3gc41133h

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One-pot transformation of alkynes into alcohols and amines with formic
acid
Jia Li, a Chao Wang,*a Dong Xue, a Yawen Wei, a and Jianliang Xiao*a,b
Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
5
DOI: 10.1039/b000000x
Alkynes are converted into alcohols and amines through a
formic acid-participated alkyne-to-ketone transformation and
transfer hydrogenation process. The reaction proceeds well
under aqueous conditions, furnishing chiral alcohols directly
10 from alkynes for the first time.
45
Introduction
Scheme 1 Oneꢀpot formic acidꢀparticipated transformation of alkynes into
alcohols and amines. General reaction conditions: alkynes (3 mmol),
HCOOH (3 mL), amines (6 mmol), S/C = 100 ꢀ 500.
The functionalisation of alkynes is a fundamental and important
class of reaction in organic synthesis. Alkynes can be converted
into carbonyl compounds or imines via hydration1 or
15 hydroamination2 reactions. However, examples of direct
transformation of alkynes into alcohols or amines are rare.
Alkyne to alcohol transformation can be achieved by
hydration/reduction processes3 or hydroboration reactions.4
Coupled hydration/reduction of alkynes only appeared recently.3
20 By combination of hydration and transfer hydrogenation catalysts,
Herzon and coꢀworkers developed a regioselective system for
alkyne to alcohol conversion.3b Transformation of alkynes to
amines can be realized through hydration/reductive amination or
hydroamination/reduction reactions.5 Examples of reductive
25 hydroamination of alkynes using a single catalyst for both
hydroamination and reduction were reported by Che,6 Gong,7
50 transformation of alkynes to alcohols and amines through a
hydration/transfer hydrogenation process, ideally using a single
catalyst for both hydration and reduction steps and cheap
hydrogen sources, e.g. formic acid or isopropanol.11
Initially, some transfer hydrogenation catalysts were screened
55 for the hydration of paraꢀmethoxylphenyl acetylene in aqueous
methanol. Unfortunately, common transfer hydrogenation
catalysts, such as RhꢀTsDPEN12 (TsꢀDPEN
=
Nꢀ(pꢀ
toluenesulfonyl)ꢀ1,2ꢀdiphenylethylenediamine) or cyclometalated
iridium complexes,13 did not catalyse this step (Table S1, entries
60 1ꢀ2, ESI†). Although [RuCl2(pꢀcymene)]2, [Cp*RhCl2]2 and
[Cp*IrCl2]2 are all active for the reaction, the systems could not
be extended to other alkyne substrates (Table S1, entries 3ꢀ6,
ESI†).
Beller,8 Djukic9 and their coꢀworkers. However,
a
hydration/reductive amination process for conversion of alkynes
into amines is unknown. In this paper, we report a new process
30 for oneꢀpot transformation of alkynes into alcohols and amines by
virtue of a formic acidꢀpromoted alkyneꢀtoꢀketone reaction
coupled with formic acidꢀparticipated transfer hydrogenation and
transfer hydrogenative reductive amination (Scheme 1).
On careful examination of the literature concerning alkyne to
65 ketone transformation, we noticed that alkynes could be
transformed into ketones with pure formic acid (Scheme 1) via a
route different from hydration reactions.14 In this reaction,
alkynes react with formic acid to form ketones with the release of
CO gas, which might pose toxicity issues for scaling up.
70 Nevertheless, considering formic acid is a hydrogen source
commonly used in transfer hydrogenation reactions, attention was
then turned to developing a one pot system in which formic acid
would react with the alkyne to give a ketone and then participate
in the ketone reduction (Scheme 1). Phenylacetylene was tested
75 in the formic acidꢀenabled alkyne to ketone transformation. As
anticipated, acetophenone was obtained with a conversion of 93%
Results and Discussion
35 Based on our experience in aqueous transfer hydrogenation
reactions,10 we were interested to devise a system for
a Key Laboratory of Applied Surface and Colloid Chemistry,
Ministry of Education and School of Chemistry and Chemical
Engineering, Shaanxi Normal University, Xi’an, 710062, China.
40 E-mail: c.wang@snnu.edu.cn; Tel: 86-29-85310840
b Department of Chemistry, University of Liverpool, Liverpool, L69
7ZD, UK, jxiao@liverpool.ac.uk
o
in 0.5 h in HCOOH at 100 C. However, addition of a transfer
hydrogenation catalyst into the pure formic acid system resulted
in no reduction of ketone, probably due to the strong acidic
80 reaction conditions.
† Electronic Supplementary Information (ESI) available: Experimental
procedures, characterisation data. See DOI: 10.1039/b000000x
This journal is © The Royal Society of Chemistry [year]
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DOI: 10.1039/C3GC41133H
Ketones and aldehydes can be reduced by aqueous transfer
hydrogenation using formic acid as hydrogen source. A recent
example was developed by our group, using the cyclometalated
The substrate scope of the systems was then examined with
different alkynes. A substrate to catalyst ratio (S/C) of 500 was
generally used for the second step. Various aromatic terminal
iridium catalysts with aqueous HCOOH/HCOONa. However, the 25 alkynes could be converted into alcohols with moderate to good
5
reaction took place only at a suitable pH.10f For example,
acetophenone was reduced to 1ꢀphenylethanol at pH 3.5 with
catalyst 1. Inspired by this study, phenylacetylene was stirred in
pure formic acid for 0.5 h at 100 oC, and then saturated HCOONa
yields (Table 1, entries 1ꢀ6). The 1ꢀparaꢀmethoxylphenyl alcohol
was obtained with low yield, probably due to the difficulty of
reduction of the corresponding ketone under the conditions
employed (Table 1, entry 3).10f Generally, substrates with
was added to adjust the pH to 3.5. After addition of 0.1 mol% of 30 electron donating substituents displayed higher activities for the
o
10 1, the mixture was stirred at 80 C for a further 6 h. To our
first step. 20 mol% of pꢀtoluenesulfonic acid monohydrate was
added to accelerate the first step for substrates with 4ꢀBr and 3ꢀCl
substituents, and a S/C of 200 was used for the 4ꢀBr substituted
substrate (Table 1, entry 4). Internal alkynes are viable substrates,
35 albeit also requiring the addition of pꢀtoluenesulfonic acid
monohydrate or a higher catalyst loading, probably due to their
steric hindrance (Table 1, entries 7ꢀ8). Aliphatic alkynes were
also examined under these conditions. However, no alcohol
product was obtained. For example, although 1ꢀoctyne could be
40 converted into 2ꢀoctanone with 84% yield in 5 h in pure HCOOH,
no alcohol product was observed after performing the second step.
Chiral alcohols can be obtained, if the formic acidꢀparticipated
alkyne to ketone transformation is coupled with asymmetric
transfer hydrogenation. The Rhꢀ(S,S)ꢀTsDPEN complex 3 is
45 known to catalyse aqueous asymmetric transfer hydrogenation10c
and was chosen to test the feasibility of this hypothesis. The
solution pH was tuned to 7 with a NaOH solution after the first
delight, 1ꢀphenylethanol was isolated with 80% yield (Scheme 2).
Scheme 2 One pot transformation of phenylacetylene to 1ꢀphenylethanol.
15 Reaction conditions: Phenylacetylene (3 mmol), HCOOH (3 mL),
HCOONa (5.6 mL, 15.5 mol/L), 1 (0.003 mmol).
Table 1 One pot transformation of alkynes into achiral alcoholsa
step and
3
was subsequently introduced.10c The transfer
hydrogenation was carried out at 40 oC at a typical S/C of 200.
Entry
1d
Product
Time (h)b
0.5/6
Yield (%)c
80
50 Table 2 One pot transformation of alkynes into chiral alcoholsa
2
3
3/6
5/6
85
52
Yield (%)c
87
ee (%)d
>99
Entry
1
Product
Time (h)b
0.5/3
OH
4e,f
5/6
5/6
86
81
Br
2
3/6
5/6
72
86
98
99
5
OH
3e,f
Br
6e
5/6
87
79
4e
5/12
5/12
86
84
95
96
7e
5/6
5 e,f
8 e,f
2/14
85
a
b
Conditions: Alkyne (3 mmol), HCOOH (3 mL), S/C = 200. Numbers
a
b
Conditions: Alkyne (3 mmol), HCOOH (3 mL), S/C = 500. Numbers
before and after the slash represent time for the first and second step,
before and after the slash represent time for the first and second step,
respectively. Isolated yield. d Determined by Chiral HPLC. TsOHꢁH2O
c
e
20 respectively. Isolated yield. d S/C = 1000. e TsOHꢁH2O (20 mol % ) was
c
(20 mol % ) was added. f S/C = 100.
added. f S/C = 200.
2
| Journal Name, [year], [vol], 00–00
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DOI: 10.1039/C3GC41133H
Table 3 One pot transformation of alkynes into aminesa
alcohol transformation, aliphatic alkynes are suitable substrates
for alkyneꢀtoꢀamine reaction. Good yields were obtained for the
two aliphatic alkynes tested (5kꢀl).
30 Conclusions
In conclusion, one pot transformation of alkynes into alcohols
and amines has been achieved by formic acidꢀenabled alkyneꢀtoꢀ
ketone conversion coupled with pHꢀregulated aqueous transfer
hydrogenation using formic acid as hydrogen source. Chiral
35 alcohols were derived from alkynes for the first time. The study
also provides the first example of transforming alkynes into
amines through an alkyneꢀtoꢀketone/reductive amination process,
which could inspire new thoughts on alkyneꢀtoꢀamine
transformations. The idea of “switch on” a reaction by tuning
40 solution pH may find applications in devising new oneꢀpot
aqueousꢀphase reactions.
HN
HN
HN
5a
5b
0.5/9 h, 70%
5c
0.5/9 h, S/C = 200, 59%
0.5/16 h,b S/C = 200, 52%
OMe
F
HN
HN
HN
5d
5e
5f
0.5/3.5 h, 75%
0.5/10 h, 63%
0.5/24 h, 62%
Experimental section
OMe
OMe
OMe
Typical procedure for transforming alkynes to achiral
alcohols
HN
HN
HN
MeO
F
45 A tube was charged with a magnetic stir bar and phenylacetylene
(3 mmol). HCOOH (3 mL, 99%) was introduced into the tube
with a syringe. The resulting mixture was bubbled with argon for
15 min. The tube was then sealed and the mixture was stirred at
100 oC for 0.5 h. Upon cooling to room temperature, the tube was
50 opened and 5.6 mL of aqueous HCOONa solution (15.5 mol/L)
was added to adjust the solution pH to 3.5. After addition of
catalyst 1 (0.003 mmol), the resulting mixture was stirred at
80 °C for 6 h. After cooling to room temperature, the reaction
mixture was transferred to a beaker containing 30 mL of MeOH
55 and the resulting mixture was basified with KOH (pH = 9~10)
and stirred for 30 min to hydrolyse any formyl ester product.
MeOH was then removed from the mixture under vacuum and the
aqueous solution was extracted with ethyl acetate. The organic
phase was washed with brine and dried over anhydrous Na2SO4.
60 After removing ethyl acetate under vacuum, the residue was
purified by flash chromatography [petroleum ether (m.p = 60~90
oC): ethyl acetate = 8:1] to afford 1ꢀphenylethanol in 80% yield.
5g
3/12 h, 75%
5h
5i
5/12 h, 86%
5/12 h, 64%
OMe
MeO
MeO
HN
NH
NH
5j
5k
2/3 h, S/C = 200, 78%
5l
5/3 h, S/C = 200, 79%
2/3 h, 20 mol% TsOH, 71%
a
Conditions: Alkyne (3 mmol), HCOOH (3 mL), amine (6 mmol), 1
b
(0.006 mmol), S/C = 500, isolated yield. Numbers before and after the
slash represent time for the first and second step, respectively (the same
for the other examples).
5
Chiral alcohols were indeed obtained with good yields and
enantioselectivities (Table 2). Terminal aromatic alkynes could
be converted to the corresponding alcohols with ees up to 99%
(Table 2, entries 1ꢀ4). An internal alkyne also reacted to afford
10 the chiral alcohol 4e in 84% yield and 96% ee in a total time of
17 h (Table 2, entry 5).
Typical procedure for transforming alkynes to chiral alcohols
A tube was charged with a magnetic stir bar and phenylacetylene
65 (3 mmol). HCOOH (3 mL , 99%) was introduced into the tube
with syringe. The resulting mixture was bubbled with argon for
15 min. The tube was then sealed and the mixture was stirred at
100 oC for 0.5 h. Upon cooling to room temperature, the tube was
opened and aqueous NaOH solution (17 mol/L) was added to
70 adjust the solution pH to 7. After addition of catalyst 3 (0.015
mmol), the resulting mixture was stirred at 40 °C for 3 h. After
cooling to room temperature, the reaction mixture was extracted
with ethyl acetate. The organic phase was washed with brine and
dried over anhydrous Na2SO4. After removing ethyl acetate under
75 vacuum, the residue was purified by flash chromatography
One pot alkyne to ketone and transfer hydrogenative reductive
amination reaction was then examined in order to produce amines
from alkynes, employing an aqueous reductive amination system
15 recently developed by our group.10e For this process, the pH was
adjusted to 4.8 for the reductive amination step.10e Upon finishing
the first step, a NaOH solution was added to adjust the pH to the
desired level, followed by the addition of catalyst 1 and amine
source. As can be seen from Table 3, primary aromatic amines
20 reacted with phenylacetylene to afford the corresponding
secondary amines with moderate to good yields (5aꢀe). An
example of aliphatic amines also worked (5f). Again, aromatic
terminal alkynes with different substituents worked well with
yields up to 86% (5gꢀi). Aromatic internal alkyne was less
25 reactive in the first step, requiring the addition of 20 mol% of pꢀ
toluenesulfonic acid monohydrate (5j). Unlike in the alkyneꢀto
o
[petroleum ether (m.p = 60~90 C): ethyl acetate = 8:1] to afford
1ꢀphenylethanol in 87% yield. The enantiomeric excess of
product was determined by chiral HPLC analysis: Chiralcel ODꢀ
This journal is © The Royal Society of Chemistry [year]
Journal Name, [year], [vol], 00–00 | 3

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DOI: 10.1039/C3GC41133H
H (hexane/iPrOH = 97/3, flow rate: 0.5 mL/min), tR (major) =
25.67 min, tS (minor) = 35.55 min, 87% ee.
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55
Typical procedure for transforming alkynes to amines
A tube was charged with a magnetic stir bar and phenylacetylene
(3 mmol). HCOOH (3 mL, 99%) was introduced into the tube
with syringe. The resulting mixture was bubbled with argon for
15 min. The tube was then sealed and the mixture was stirred at
100 oC for 0.5 h. Upon cooling to room temperature, the tube was
opened and 4.7 mL of aqueous NaOH solution (17 mol/L) was
10 added to adjust the solution pH to 4.8. After addition of catalyst 1
(0.006 mmol) and pꢀanisidine (6 mmol), the resulting mixture
was stirred at 80 °C for 3.5 h. After cooling to room temperature,
aqueous HCl solution (3 mol/L) was added to adjust solution pH
to 2ꢀ3 and the mixture was stirred at room temperature for 10 min
15 to hydrolyse any imines. The resulting mixture was then basified
with NaOH solution (6 mol/L) to pH around 9ꢀ10 and extracted
with ethyl acetate. The organic phase was washed with brine and
dried over anhydrous Na2SO4. After removing ethyl acetate under
vacuum, the residue was purified by flash chromatography
20 [petroleum ether (m.p = 60~90 oC): ethyl acetate = 40:1] to afford
4ꢀmethoxyꢀNꢀ(1ꢀphenylethyl)aniline in 75% yield.
5
60
65
70
75
Acknowledgements
We are grateful for the financial support of the National Science
25 Foundation of China (21103102), Program for Changjiang
Scholars and Innovative Research Team in University (IRT
1070), the Cheung Kong Scholar Programme, the Fundamental
Research Funds for the Central Universities (GK200902009) and
the Distinguished Doctoral Research Found from Shaanxi
30 Normal University (S2011YB02).
80
85
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4
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Green Chemistry
Page 6 of 6
View Article Online
DOI: 10.1039/C3GC41133H
Graphic Abstract:
Alcohols and amines are directly produced from alkynes through a one-pot formic
acid-participated alkyne-to-ketone transformation and transfer hydrogenation process.