Formal reductive addition of acetonitrile to aldehydes and ketones

Article abstract of DOI:10.1039/c8ob01992d

An efficient and highly productive rhodium-catalyzed method for the synthesis of nitriles employing aldehydes or ketones, methyl cyanoacetate, water and carbon monoxide as starting materials has been developed. Simple rhodium chloride without any ligands can be used. The fine tuning of the substrate can lead to the activity higher than 5000 TON.

Full text of DOI:10.1039/c8ob01992d

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Formal reductive addition of acetonitrile to aldehydes and ketones
Karim Muratov,a § Ekaterina Kuchuk,a § Sreekumar Vellalath,b Oleg I. Afanasyev,a Alexei
P. Moskovets,a Gleb Denisova and Denis Chusov*,a
aNesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,
Moscow 119991, Russia
bDepartment of Chemistry and Biochemistry, Baylor University, Waco, TX 76798, USA
§ These authors are contributed equally
† Dedicated to Professor Yuri N. Belokon (Nesmeyanov Institute, Moscow) on the
occasion of his 80th birthday.
Eꢀmail: chusov@ineos.ac.ru or denis.chusov@gmail.com
Abstract
An efficient and highly productive rhodium-catalyzed method for nitriles synthesis employing aldehydes
or ketones, methyl cyanoacetate, water and carbon monoxide as starting materials has been developed.
Simple rhodium chloride without any ligands can be used. The fine tuning for the substrate can lead to
the activity higher than 5000 TON.
INTRODUCTION
Nitriles are versatile, useful building blocks for organic synthesis1. Their utility is
amply demonstrated as solvents1a, initiators of radical chain polymerization1b, raw
materials in the production of fiberꢀforming polymers1c (Nylon) and among other
1dꢀf. Nitriles are also frequently encountered structural subunits in numerous
bioactive natural products1g and pharmaceuticals1h. Examples of bioactive agents
include Saxagliptin, Odanacatib, Vildagliptine and precursors of Pregabalin6b and
human renin inhibitors6b (Figure 1). In addition, nitriles have occupied a certain
niche in organic synthesis2 being the precursors of amines2a, carbonyl
compounds2a and various heterocyclic substances2b,c,d,e. The methods which
have been devised for the synthesis of alkyl nitriles via CꢀC bond formation
include3 borrowingꢀhydrogen approach3a, radical path3b, alkylation of active
methylene compounds with alkyl halides3c and nucleophilic substitution in alkyl
halides3d. Other recent approaches4 for the synthesis of aryl and alkyl nitriles are
deacylative CꢀC cleavage4a, transoximation approach4b, ammoxidation of
methylarenes4c, transnitrilation4d and among other5. Arguably, the reductive

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alkylation of active methylene compounds is one of the most direct methods for
the synthesis of nitriles. Although different heterogeneous and
Figure 1. Nitriles used in medicine, in textile industry, agrochemistry.
homogeneousꢀcatalyzed variants of this reaction have been suggested in recent
years, there is paucity in tandem reductive alkylation protocols of active
methylene compounds with reductants other than molecular hydrogen5b,6
.
Reported procedures for oneꢀpot reductive condensation involve most often
metalꢀcatalyzed processes (Rh6a,b, Pd5b,5j, Pt5b). The abovementioned protocols
are riddled with some drawbacks. For example, the main drawback of the use of
alkyl halides in alkylation of active methylene compounds is their low selectivity
causing overalkylation. Also, HCN and cyanide salts that are often used to
prepare nitriles7 are very toxic (KCN: LD50 5–10 mg/kg; malononitrile: LD50 14
mg/kg). Besides, the abovementioned approaches in many cases have low atomꢀ
efficiency, low step economy or low selectivity and require special reagents
(boronic derivatives and etc.). The classical approach also suffers from narrow

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substrate scope, switching reaction from pꢀmethoxybenzaldehyde to pꢀ
methylbenzaldehyde decreases the chemical yield (62% to 19%)8 (Scheme 1).
Scheme 1. Classical approach
At the same time, approaches involving the use of CO as a reducing agent or CO
coupled with water proved to be atom efficient and very selective6,9. In particular,
Denmark et al. have recently developed method of coupling of active methylene
with carbonyl compounds having an indisputable advantage of mild reaction
conditions6c. Recently, our group developed a direct approach towards nitriles
utilizing aldehydes, methyl cyanoacetate, water and CO as starting materials6a.
Despite good yields, these methods have their own limitations such as relatively
high catalytic loading (1ꢀ3 mol%). Since the ubiquity of carbonyl compounds is
provided by their availability from oil and crude oil products by hydroformylation
or GattermanꢀKoch methodology, formal reductive addition of acetonitrile to
aldehydes and ketones employing the reducing power of carbon monoxide could
provide practical, atomꢀ and stepꢀeconomical method for the nitrile synthesis.
Given the importance of nitriles and the paucity of formal reductive addition
routes to these intermediates, we sought to develop more general and low
catalyst loading method for their synthesis.
RESULTS AND DISCUSSION
Our studies commenced with an experiment in which pꢀtolylaldehyde
1 and
methyl cyanoacetate (NCCH2COOMe: LD50 3062 mg/kg, one of the highest
2
values among cyanide derivatives) were exposed to CO in the presence of a
catalytic amount of (1 mol %) RhCl3—3H2O in MeOH containing two equivalents of
o
water. A facile reaction occurred at 160 C under CO pressure of 50 bar and
obtained a mixture
3 & 4 in 1:1 ratio (Table 1, entry 1). Next, we investigated the
effect of different solvents (Table 1, entries 2ꢀ5) but MeOH along with water
remain superior (Table 1, entries 1 & 3) and was chosen for subsequent studies.
An increase in the amount of water was advantageous to the formation of the
product
4 (Table 1, entries 1, 6 ꢀ 7). Furthermore, extending the reaction time to 6

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hours furnished product
4 in 77% (Table 1, entry 8). Furthermore, homogeneous
catalysts including those have shown excellent results in reductive amination9i
failed to improve the yield (Table 1, entries 11ꢀ13). Though [(Cod)RhCl]2,
afforded
cost. Interestingly, when the catalytic loading of RhCl3—3H2O was reduced to
0.5% or 0.2% the yield of was increased up to 85% (Table 1, entries 14 and
4 in 87% yield, however, we refrained from its use due to its rather high
4
15), which is in the level of the catalytic performance of [(Cod)RhCl]2. With the
optimal reaction conditions in hand, we set out to explore the generality of the
procedure using both aromatic and aliphatic aldehydes.
Table 1. Optimization of the reaction conditions
#
Catalyst
Solvent
Water, eq
3a, %
4a, %
1
2
3
4
5
6
7
RhCl3—3H2O
RhCl3—3H2O
RhCl3—3H2O
RhCl3—3H2O
RhCl3—3H2O
RhCl3—3H2O
RhCl3—3H2O
MeOH
THF
2
2
43
43
41
47
22
16
68
71
24
H2O
50
2
0
EtOH
iPrOH
MeOH
MeOH
15 (+48)b
30 (+38)c
24
2
5
10
12
8d
RhCl3—3H2O
MeOH
5
4
77
9
[(C4Et4)Rh(pꢀxylene)]PF6
[(Cod)RhCl]2
MeOH
MeOH
5
5
63
9
16
87
10
11
12
IndRhCp PF6
Rh2(tfa)4
MeOH
MeOH
5
5
43
4
17
78
13
[Cp*RhCl2]2
RhCl3—3H2O
RhCl3—3H2O
MeOH
MeOH
MeOH
5
5
5
6
1
1
66
82
85
14e
15f
a Yields were determined by NMR with internal standard,b,c transesterification product with solvent is observed, d 6 hours, e 0.5 mol%
of the catalyst, 6 hours, f 0.2 mol% of the catalyst, 6 hours.
The methodology tolerates a wide range of aldehydes with various electronic
nature and substituents. Orthoꢀ (
benzaldehydes transformed into nitriles in very good yields (>80%). Electron rich
) and electron deficient benzaldehydes ( ) and 1ꢀnaphthaldehyde (13) gave
7), metaꢀ (6) and paraꢀmethoxy (5) substituted
(5
8, 9
essentially the same good results. Slightly worse performance was observed for
3ꢀbromoꢀ4ꢀmethoxyꢀ (10), 3ꢀphenoxyꢀ (12) and 4ꢀhydroxyꢀ benzaldehydes (11).
We were especially intrigued to find that aliphatic aldehydes were competent

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substrates. Among 2ꢀphenyl (15) and 3ꢀphenylpropionic (14) aldehydes the latter
gave better yield. It should be noted that functional group tolerance is one of the
key beneficial features of this transformation enabling the synthesis of halogen
(Br, Cl) as well as OHꢀfunctionalized nitriles (
8ꢀ11). Importantly, suitability of
ketones for this reaction has been exemplified by using 4ꢀphenylꢀ2ꢀbutanone (17
)
and cyclohexanone (18), cyclopentanone (19), cyclobutanone (20). For ketones,
a slightly different optimization condition was chosen (Scheme 2). It should be
noted that preparation of nitrile derivatives from ketones is less common than
from aldehydes10. For the best of our knowledge, there was no examples of oneꢀ
step formal addition of acetonitrile to ketones.
Scheme 2. Scope of aldehydes and ketones used in the reaction

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NMR yield, isolated yield in parenthesis.a0.02 mol% RhCl3, b1.5 eq. of methyl cyanoacetate, 1 eq. of water, 2 mol% RhCl3—3H2O,
c1.5 eq. of methyl cyanoacetate, 2 eq. of water, 2 mol% RhCl3—3H2O
Further studies have revealed the superiority of our strategy compared to
conventional reduction systems (NaBH4, H2)11. Changing the reducing agent to
NaBH4 dramatically reduces selectivity of the process, affording no product in the
reaction mixture. As far as the reduction with H2 is concerned, it provides mixture of
unidentified products with formation of the desired nitrile in 20% yield (Scheme 3).
Scheme 3. Comparison of selectivity of different reducing agents

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Conditions: a 0.2 mol% RhCl3—3H2O, 417 mol% NaBH4, 24h, 65oC, b 0.2 mol% RhCl3—3H2O, 24h, 160 oC, 50 bar CO, c 0.2 mol%
RhCl3—3H2O, 24h, 160 oC, 50 bar H2
The efficiency of this rather low catalyst loading reductive addition was further
demonstrated in the case of isobutyraldehyde. It was found that catalytic system
consisting of RhCl3—3H2O is quite stable and very low catalyst loadings (100 ppm)
could be achieved producing the corresponding nitrile 16 with a TON of 5600 (the
average of two experiments) (Scheme 4).
Scheme 4. Testing the catalytic activity
The FTꢀIR experiments show two absorption bands at 2001 and 2076 cmꢀ1 (see
SI) which corresponds to the rhodium carbonyl intermediate. These results also
correlate with our previous experiments13, where we monitored formation rhodium
carbonyl complex and subsequent formation of rhodium hydride (cf. D, scheme
5). On the basis of experiments discussed in this article and our previous
reports6a,b, a plausible process of the tandem catalytic reductive addition is
depicted in Scheme 5. The addition of methyl cyanoacetate to the carbonyl
compound provides the alcohol
found that preformed alkene reacts much slower under the reaction conditions
(see SI). Alternatively, RhCl3 catalysed deoxygenation of the alcohol followed
by the reduction affords ester . The hydrolysis of the ester (see SI) and a late
delivers the alkyl nitrile (scheme
A. The alcohol A could deliver alkene G but we
G
A
E
E
stage decarboxylation resultant carboxylic acid
5).
F
Scheme 5. Tandem catalytic process

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CONCLUSION
In conclusion, we have developed an easy oneꢀstep procedure for the formal
reductive addition of acetonitrile to aldehydes with a TON 365ꢀ5600 and ketones.
To the best of our knowledge, this TON exceeds any other existing protocols for
this type of reaction. Furthermore, remarkable chemoselectivity was achieved in
the reductive addition of aldehydes containing chlorine, bromine or hydroxy
groups. Given the ready availability of rhodium chloride precatalyst, aldehydes or
ketones and cyanoacetates, we anticipate further applications of this
methodology.
EXPERIMENTAL SECTION
General methods and materials
Unless otherwise stated, all reagents were purchased from commercial suppliers and
9i
used without further purification. Rhodium complexes [(C4Et4)Rh(pꢀxylene)]PF6 ,
12a
IndRhCpPF6 were synthesized according to published procedures. For all reactions,
distilled water was used. Carbon monoxide of >98% purity was obtained from NII KM
(Moscow, Russia). Isolation of products was performed by column chromatography
1
(Acros Organics, silica gel 0.06ꢀ0.200 mm). The H and 13C NMR spectroscopic data
were recorded with Bruker AVꢀ300, AV400, and AVꢀ600 spectrometers at ambient
temperature. Chemical shifts are reported in parts per million relative to CHCl3 (7.26

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1
and 77.16 ppm for H and 13C respectively). Chemical shifts δ are reported in ppm
relative to the solvent resonance signal as an internal standard. The following
abbreviations were used to designate chemical shift multiplicities: s = singlet, d =
doublet, t = triplet, q = quartet, sept = septet, m = multiplet, br = broad; coupling
constants are given in Hertz (Hz). GC detection was performed on GC Chromatec
Crystall 5000.2.
General procedure for synthesis of nitriles
10 mL stainlessꢀsteel autoclave was charged with the catalyst (0.02–2 mol%),
methanol, methyl cyanoacetate, water and the carbonyl compound. Catalyst
should be weigh better in a solid form than be added as an aliquot to obtain about
5ꢀ10% more product according to NMR yield. The autoclave was sealed, flushed
3 times with 10 bar of CO, and then charged with 50 bar CO. The reactor was
placed into a preheated to 160 °C oil bath. After 24 h, the reactor was cooled to
room temperature and depressurized. The reaction mixture was transferred to a
flask, and the autoclave was washed with dichloromethane (2 × 1 mL). The
reaction mixture and the dichloromethane rinsings were combined and then
concentrated on a rotary evaporator, extracted with dichloromethane from water,
solvent was removed under reduced pressure and the residue was analyzed by
NMR. The residue was purified by column chromatography on silica gel.
Reaction of 4-chlorobenzaldehyde with NaBH4
To a stirred solution of RhCl3—3H2O (2.16 mg; 8.2 ꢁmol; 0.2 mol%), 4ꢀ
chlorobenzaldehyde (576 mg; 4.10 mmol; 100 mol%), methyl cyanoacetate (362.9 ꢁl;
407.5 mg; 4.11 mmol; 100 mol%), methanol (2 ml) and water (367.2 ꢁl; 367.2 mg; 20.40
mmol; 497 mol%) in 25 ml flask with reflux condenser was added NaBH4 (647.4 mg;
17.11 mmol; 417 mol%) and stirred for 24h at 650C. The reaction mixture was filtered,
the flask was washed with dichloromethane (2 × 1 mL). The reaction mixture and the
dichloromethane rinsings were combined and then concentrated on a rotary evaporator,
extracted with dichloromethane from water, solvent was removed under reduced
pressure and the residue was analyzed by NMR (no product was observed).
Reaction of 4-chlorobenzaldehyde with H2
A 10 ml stainless steel autoclave was charged with RhCl3—3H2O (0.2 mg; 0.76 ꢁmol; 0.2
mol%), 4ꢀchlorobenzaldehyde (50 mg; 0.36 mmol; 100 mol%), methanol (356 ꢁl),
methyl cyanoacetate (31 ꢁl; 0.35 mmol; 97 mol%) and water (32 ꢁl; 1.78 mmol; 494

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mol%). The autoclave was sealed, flushed 3 times with 10 bar of H2, and then charged
with 50 bar H2. The reactor was placed into a preheated to 160 °C oil bath. After 24 h,
the reactor was cooled to room temperature and depressurized. The reaction mixture
was transferred to a flask, and the autoclave was washed with dichloromethane (2 × 1
mL). The reaction mixture and the dichloromethane rinsings were combined and then
concentrated on a rotary evaporator, extracted with dichloromethane from water,
solvent was removed under reduced pressure and the residue was analyzed by NMR
(20% of the product).
3-(p-tolyl)propanenitrile (4)
Synthesis was accomplished according to the general procedure using RhCl3—3H2O
(0.56 mg; 2.1 ꢁmol; 0.2 mol%), 4ꢀmethylbenzaldehyde (125 ꢁl; 127.4 mg; 1.06 mmol;
100 mol%), methanol (475 ꢁl), methyl cyanoacetate (94.1 ꢁl; 105.7 mg; 1.07 mmol; 101
mol%) and water (95.2 ꢁl; 95.2 mg; 5.28 mmol; 498 mol%). 86% NMR yield.
Purification: column chromatography, eluent hexane/ethyl acetate 30/1 (Rf = 0.18).
Isolated as colourless oil ꢀ 68% (105 mg). The obtained NMR data was in agreement
with the literature report12b
.
1H NMR (300 MHz, CDCl3) δ 7.20 – 7.10 (m, 4H), 2.92 (t, J = 7.4 Hz, 2H), 2.60 (t, J =
7.4 Hz, 2H), 2.35 (s, 3H). 13C NMR (101 MHz, CDCl3) δ 136.9, 135.1, 129.6, 128.2,
119.3, 31.2, 21.1, 19.5
3-(4-methoxyphenyl)propanenitrile (5)
Synthesis was accomplished according to the general procedure using RhCl3—3H2O
(0.56 mg; 2.1 ꢁmol; 0.21 mol%), 4ꢀmethoxybenzaldehyde (136 ꢁl; 152.2 mg; 1.12
mmol; 100 mol%), methanol (475 ꢁl), methyl cyanoacetate (94.1 ꢁl; 105.6 mg; 1.07
mmol; 96 mol%) and water (95.2 ꢁl; 95.2 mg; 5.28 mmol; 472 mol%). 86% NMR yield.
Purification: column chromatography, eluent hexane/ethyl acetate 10/1 (Rf = 0.18).
Isolated as paleꢀyellow oil ꢀ 74% (127 mg). The obtained NMR data was in agreement
with the literature report6b.
1H NMR (300 MHz, CDCl3) δ 7.15 (d, J = 8.5 Hz, 2H), 6.87 (d, J = 8.5 Hz, 2H), 3.79 (s,
3H), 2.89 (t, J = 7.3 Hz, 2H), 2.57 (t, J = 7.3 Hz, 2H). 13C NMR (75 MHz, CDCl3) δ
158.7, 130.2, 129.4, 119.4, 114.2, 55.3, 30.7, 19.7
3-(3-methoxyphenyl)propanenitrile (6)

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Synthesis was accomplished according to the general procedure using RhCl3—3H2O
(0.25 mg 0.95 ꢁmol; 0.2 mol%), 3ꢀmethoxybenzaldehyde (58 ꢁl; 64.8 mg; 0.48 mmol;
100 mol%), methanol (238 ꢁl), methyl cyanoacetate (42 ꢁl; 47.1 mg; 0.48 mmol; 100
mol%) and water (42.5 ꢁl; 42.5 mg; 2.36 mmol; 491 mol%). 83% NMR yield.
Purification: column chromatography, eluent hexane/ethyl acetate 10/1 (Rf = 0.17).
Isolated as paleꢀyellow oil ꢀ 68% (53 mg). The obtained NMR data was in agreement
with the literature report12c.
1H NMR (300 MHz, CDCl3) δ 7.32 (dd appears as t, J = 7.8 Hz, 1H), 6.93 – 6.81 (m,
13
3H), 3.87 (s, 3H), 2.99 (t, J = 7.4 Hz, 2H), 2.67 (t, J = 7.4 Hz, 2H). C NMR (75 MHz,
CDCl3) δ 159.9, 139.7, 130.0, 120.6, 119.3, 114.1, 112.5, 55.3, 31.6, 19.3
3-(2-methoxyphenyl)propanenitrile (7)
Synthesis was accomplished according to the general procedure using RhCl3—3H2O
(0.56 mg 2.1 ꢁmol; 0.2 mol%), 3ꢀmethoxybenzaldehyde (144.5 mg; 1.06 mmol; 100
mol%), methanol (475 ꢁl), methyl cyanoacetate (92.4 ꢁl; 103.8 mg; 1.05 mmol; 99
mol%) and water (93.5 ꢁl; 93.5 mg; 5.19 mmol; 490 mol%). 88% NMR yield.
Purification: gradient column chromatography, eluent hexane/ethyl acetate from 30/1 (Rf
= 0.14) to 15/1 (Rf = 0.21). Isolated as paleꢀyellow oil ꢀ 74% (125 mg). The obtained
NMR data was in agreement with the literature report12d
.
1H NMR (300 MHz, CDCl3) δ 7.33 (dd appears as t, J = 7.8 Hz, 1H), 7.25 (d, J = 7.4 Hz,
1H), 7.06 – 6.89 (m, 2H), 3.90 (s, 3H), 3.02 (t, J = 7.4 Hz, 2H), 2.69 (t, J = 7.4 Hz, 2H).
13C NMR (75 MHz, CDCl3) δ 157.3, 130.3, 128.7, 126.4, 120.7, 119.8, 110.4, 55.2, 27.1,
17.5
3-(4-chlorophenyl)propanenitrile (8)
Synthesis was accomplished according to the general procedure using RhCl3—3H2O (0.2
mg 0.76 ꢁmol; 0.2 mol%), 4ꢀchlorobenzaldehyde (50 mg; 0.36 mmol; 100 mol%),
methanol (260 ꢁl), methyl cyanoacetate (31 ꢁl; 34.8 mg; 0.35 mmol; 97 mol%) and
water (32 ꢁl; 32 mg; 1.80 mmol; 500 mol%). 86% NMR yield. Purification: column
chromatography, eluent hexane/ethyl acetate 20/1 (Rf = 0.13). Isolated as colourless oil
ꢀ 81% (47.1 mg). The obtained NMR data was in agreement with the literature report12d
.

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1H NMR (300 MHz, CDCl3) δ 7.31 (d, J = 8.3 Hz, 2H), 7.17 (d, J = 8.3 Hz, 2H), 2.92 (t, J
= 7.3 Hz, 2H), 2.60 (t, J = 7.3 Hz, 2H). 13C NMR (75 MHz, CDCl3) δ 136.5, 133.2, 129.8,
129.1, 119.0, 30.9, 19.4
3-(2-chlorophenyl)propanenitrile (9)
Synthesis was accomplished according to the general procedure using RhCl3—3H2O
(0.22 mg 0.83 ꢁmol; 0.23 mol%), 2ꢀchlorobenzaldehyde (40 ꢁl, 50 mg; 0.36 mmol; 100
mol%), methanol (250 ꢁl), methyl cyanoacetate (31 ꢁl; 34.8 mg; 0.35 mmol; 97 mol%)
and water (32 ꢁl; 32 mg; 1.80 mmol; 500 mol%). 83% NMR yield. Purification: column
chromatography, eluent hexane/ethyl acetate 20/1 (Rf = 0.21). Isolated as colourless oil
ꢀ 68% (39.3 mg). The obtained NMR data was in agreement with the literature report6a.
1H NMR (300 MHz, CDCl3) δ 7.39 – 7.30 (m, 1H), 7.30 – 7.15 (m, 3H), 3.05 (t, J = 7.3
Hz, 2H), 2.64 (t, J = 7.3 Hz, 2H). 13C NMR (75 MHz, CDCl3) δ 135.6, 133.8, 130.9,
129.9, 129.0, 127.4, 119.0, 29.7, 17.5
3-(3-bromo-4-methoxyphenyl)propanenitrile (10)
Synthesis was accomplished according to the general procedure using RhCl3—3H2O
(0.17 mg 0.65 ꢁmol; 0.2 mol%), 3ꢀbromoꢀ4ꢀmethoxybenzaldehyde (70 mg; 0.326 mmol;
100 mol%), methanol (250 ꢁl), methyl cyanoacetate (28.7 ꢁl; 32.2 mg; 0.33 mmol; 100
mol%) and water (29 ꢁl; 29 mg; 1.61 mmol; 494 mol%). 75% NMR yield. Purification:
gradient column chromatography, eluent hexane/ethyl acetate from 25/1 (Rf = 0.05) to
10/1. Isolated as paleꢀyellow oil ꢀ 67% (52.2 mg). The obtained NMR data was in
agreement with the literature report6a.
1H NMR (300 MHz, CDCl3) δ 7.40 (s, 1H), 7.15 (d, J = 8.4 Hz, 1H), 6.85 (d, J = 8.4 Hz,
13
1H), 3.87 (s, 3H), 2.86 (t, J = 7.2 Hz, 2H), 2.58 (t, J = 7.2 Hz, 2H). C NMR (75 MHz,
CDCl3) δ 155.1, 133.1, 131.6, 128.5, 119.0, 112.2, 111.8, 56.3, 30.3, 19.6
3-(4-hydroxyphenyl)propanenitrile (11)
Synthesis was accomplished according to the general procedure using RhCl3—3H2O
(0.28 mg 1.06 ꢁmol; 0.2 mol%), 4ꢀhydroxybenzaldehyde (65 mg; 0.53 mmol; 100
mol%), methanol (280 ꢁl), methyl cyanoacetate (47 ꢁl; 52.8 mg; 0.53 ꢁmol; 100 mol%)
and water (48 ꢁl; 48 mg; 2.66 mmol; 501 mol%). 76% NMR yield. Purification: gradient
column chromatography, eluent hexane/ethyl acetate from 10/1 to 5/1 (Rf = 0.09).

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Isolated as paleꢀyellow oil ꢀ 66% (51.4 mg). The obtained NMR data was in agreement
with the literature report12e
.
1H NMR (300 MHz, CDCl3) δ 7.08 (d, J = 8.4 Hz, 2H), 6.79 (d, J = 8.4 Hz, 2H), 6.4 –
6.05 (br s, 1H), 2.86 (t, J = 7.1 Hz, 2H), 2.59 (t, J = 7.1 Hz, 2H). 13C NMR (101 MHz,
CDCl3) δ 155.1, 129.8, 129.5, 119.5, 115.8, 30.6, 19.7
3-(3-phenoxyphenyl)propanenitrile (12)
Synthesis was accomplished according to the general procedure using RhCl3—3H2O
(0.58 mg 2.2 ꢁmol; 0.2 mol%), 3ꢀphenoxybenzaldehyde (190 ꢁl; 217.9 mg; 1.10 mmol;
100 mol%), methanol (475 ꢁl), methyl cyanoacetate (97.5 ꢁl; 109.5 mg; 1.10 mmol; 100
mol%) and water (98.6 ꢁl; 98.6 mg; 5.48 mmol; 498 mol%). 77% NMR yield.
Purification: column chromatography, eluent hexane/ethyl acetate 10/1 (Rf = 0.22).
Isolated as colourless oil ꢀ 70% (171.8 mg). The obtained NMR data was in agreement
with the literature report12f.
1H NMR (400 MHz, CDCl3) δ 7.43 – 7.28 (m, 3H), 7.14 (t, J = 7.4 Hz, 1H), 7.06 – 6.88
(m, 5H), 2.93 (t, J = 7.4 Hz, 2H), 2.61 (t, J = 7.4 Hz, 2H). 13C NMR (101 MHz, CDCl3) δ
157.8, 156.9, 140.0, 130.3, 129.9, 123.6, 123.1, 119.1, 119.0, 118.6, 117.5, 31.4, 19.2
3-(naphthalen-1-yl)propanenitrile (13)
Synthesis was accomplished according to the general procedure using RhCl3—3H2O
(0.52 mg; 2 ꢁmol; 0.2 mol%), 1ꢀnaphthaldehyde (134 ꢁl; 154.1 mg; 0.99 mmol; 100
mol%), methanol (475 ꢁl), methyl cyanoacetate (87.4 ꢁl; 98.1 mg; 0.99 mmol; 100
mol%) and water (88.5 ꢁl; 88.5 mg; 4.91 mmol; 497 mol%). 83% NMR yield.
Purification: column chromatography, eluent hexane/ethyl acetate 12/1 (Rf = 0.26).
Isolated as paleꢀyellow oil ꢀ 76% (137 mg). The obtained NMR data was in agreement
with the literature report6a.
1H NMR (300 MHz, CDCl3) δ 7.98 – 7.88 (m, 2H), 7.81 (d, J = 8.0 Hz, 1H), 7.66 – 7.50
(m, 2H), 7.49 – 7.38 (m, 2H), 3.43 (t, J = 7.6 Hz, 2H), 2.76 (t, J = 7.6 Hz, 2H). 13C NMR
(75 MHz, CDCl3) δ 134.0, 133.9, 131.1, 129.2, 128.2, 126.6, 126.0, 125.7, 122.7, 119.3,
28.8, 18.5
5-phenylpentanenitrile (14)

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Synthesis was accomplished according to the general procedure using RhCl3—3H2O (0.6
mg 2.3 ꢁmol; 0.2 mol%), 3ꢀphenylpropionaldehyde (142 ꢁl; 143.4 mg; 1.07 mmol; 100
mol%), methanol (475 ꢁl), methyl cyanoacetate (100.8 ꢁl; 113.2 mg; 1.14 mmol; 106
mol%) and water (102 ꢁl; 102 mg; 5.67 mmol; 530 mol%). >96% NMR yield.
Purification: column chromatography, eluent hexane/ethyl acetate 10/1 (Rf = 0.28).
Isolated as colourless oil ꢀ 65% (110 mg). The obtained NMR data was in agreement
with the literature report12g
.
1H NMR (600 MHz, CDCl3) δ 7.36 (dd appears as t, J = 7.6 Hz, 2H), 7.27 (t, J = 7.6 Hz,
1H), 7.24 (d, J = 7.6 Hz, 2H), 2.70 (t, J = 7.6 Hz, 2H), 2.35 (t, J = 7.2 Hz, 2H), 1.86 –
1.79 (m, 2H), 1.75 – 1.68 (m, 2H). 13C NMR (101 MHz, CDCl3) δ 141.2, 128.3, 128.2,
125.9, 119.6, 34.8, 30.1, 24.7, 16.9
4-phenylpentanenitrile (15)
Synthesis was accomplished according to the general procedure using RhCl3—3H2O
(0.55 mg 2.1 ꢁmol; 0.2 mol%), 2ꢀphenylpropionaldehyde (132 ꢁl; 132.2 mg; 0.99 mmol;
100 mol%), methanol (475 ꢁl), methyl cyanoacetate (92.4 ꢁl; 103.7 mg; 1.05 mmol; 106
mol%) and water (93.5 ꢁl; 93.5 mg; 5.19 mmol; 524 mol%). 73% NMR yield.
Purification: column chromatography, eluent hexane/ethyl acetate 10/1 (Rf = 0.31).
Isolated as colourless oil ꢀ 63% (99 mg). The obtained NMR data was in agreement with
the literature report12h
.
1H NMR (400 MHz, CDCl3) δ 7.37 (dd appears as t, J = 7.3 Hz, 2H), 7.28 (d, J = 7.3 Hz,
1H), 7.23 (d, J = 7.3 Hz, 2H), 2.97 – 2.86 (m, 1H), 2.36 – 1.86 (m, 4H), 1.35 (d, J = 7.0
Hz, 3H). 13C NMR (101 MHz, CDCl3) δ 144.6, 128.8, 126.9, 126.8, 119.7, 38.9, 33.5,
21.9, 15.4
Experiment with two consecutive reaction cycles
A 20 ml stainless steel autoclave was charged with RhCl3—3H2O (0.22 mg; 8.3 ꢁmol;
0.02 mol%), isobutyraldehyde (378.4 ꢁl; 298.9 mg; 4.15 mmol; 100 mol%), methanol
(2080 ꢁl), methyl cyanoacetate (368.4 ꢁl; 413.7 mg; 4.18 mmol; 101 mol%) and water
(372.8 ꢁl; 372.8 mg; 20.70 mmol; 499 mol%). The autoclave was sealed and charged
with 50 bar CO. The reactor was placed into a preheated to 160 °C oil bath. After 24 h,
the reactor was cooled to liquid nitrogen temperature and depressurized. Then 90 ꢁl of
mesitylene was added in to the reaction mixture and 30 ꢁl of solution was taken from

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reactor and analyzed by NMR. 82% NMR yield. Then autoclave was charged with
isobutyraldehyde (378.4 ꢁl; 298.9 mg; 4.15 mmol; 100 mol%), methyl cyanoacetate
(368.4 ꢁl; 413.7 mg; 4.18 mmol; 101 mol%) and water (74.5 ꢁl; 74.5 mg; 4.14 mmol;
100 mol%), sealed and charged with 50 bar CO. The reactor was placed into a
preheated to 160 °C oil bath. After 24 h, the reactor was cooled to liquid nitrogen
temperature and depressurized. Then 41.5 mg of 4ꢀdinitrobenzene was added into the
reaction mixture and 30 ꢁl of solution was taken from reactor and analyzed by NMR.
The total TON = 5700. The obtained NMR data for 16 was in agreement with the
literature report12i.
1H NMR (400 MHz, CDCl3) δ 2.31 (t, J = 7.4 Hz, 2H), 1.77 – 1.61 (m, 1H), 1.51 (dt
appears as q, J = 7.4 Hz, 2H), 0.90 (d, J = 6.6 Hz, 6H). 13C NMR (101 MHz, CDCl3) δ
120.0, 33.9, 27.2, 21.7, 15.1
3-methyl-5-phenylpentanenitrile (17)
Synthesis was accomplished according to the general procedure using RhCl3—3H2O (2
mg; 7.6 ꢁmol; 2 mol%), 4ꢀphenylbutanꢀ2ꢀone (56.9 ꢁl; 56.3 mg; 0.38 mmol; 100 mol%),
methanol (200 ꢁl), methyl cyanoacetate (50.3 ꢁl; 56.4 mg; 0.57 mmol; 150 mol%) and
water (6.8 ꢁl; 6.8 mg; 0.38 mmol; 100 mol%). No extraction from water was needed.
76% NMR yield. Purification: column chromatography, eluent hexane/DCM 2/1 (Rf =
0.4). Isolated as colourless oil ꢀ 68% (45 mg). The obtained NMR data was in
agreement with the literature report12b
.
1H NMR (400 MHz, CDCl3) δ 7.35 – 7.27 (m, 2H), 7.24 – 7.16 (m, 3H), 2.80 – 2.55 (m,
2H), 2.41 – 2.21 (m, 2H), 1.96 – 1.85 (m, 1H), 1.84 – 1.72 (m, 1H), 1.70 – 1.62 (m, 1H),
1.13 (d, J = 6.7 Hz, 3H). 13C NMR (101 MHz, CDCl3) δ 141.5, 128.6, 128.4, 126.2,
118.8, 37.6, 33.2, 30.0, 24.6, 19.5
2-cyclohexylacetonitrile (18)
Synthesis was accomplished according to the general procedure using RhCl3—3H2O (2
mg; 7.6 ꢁmol; 2 mol%), cyclohexanone (39.3 ꢁl; 37.3 mg; 0.38 mmol; 100 mol%),
methanol (200 ꢁl), methyl cyanoacetate (50.3 ꢁl; 56.4 mg; 0.57 mmol; 150 mol%) and
water (6.8 ꢁl; 6.8 mg; 0.38 mmol; 100 mol%). No extraction from water was needed.
68% NMR yield. Purification: column chromatography, eluent hexane/DCM 1/1.
Detection with GCꢀFID. Isolated as colourless oil ꢀ 60% (28 mg). The obtained NMR
data was in agreement with the literature report12j.

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1H NMR (300 MHz, CDCl3) δ 2.23 (d, J = 5.3 Hz, 2H), 1.94 – 1.56 (m, 6H), 1.38 – 0.94
(m, 5H). 13C NMR (101 MHz, CDCl3) δ 119.1, 34.9, 32.5, 25.8, 25.8, 24.9
2-cyclopentylacetonitrile (19)
Synthesis was accomplished according to the general procedure using RhCl3—3H2O (7.9
mg; 30 ꢁmol; 2 mol%), cyclopentanone (132.5 ꢁl; 126.0 mg; 1.5 mmol; 100 mol%),
methanol (800 ꢁl), methyl cyanoacetate (198.7 ꢁl; 222.8 mg; 2.25 mmol; 150 mol%) and
water (27 ꢁl; 27 mg; 1.5 mmol; 100 mol%). No extraction from water was needed. 53%
GC yield. Purification: column chromatography, eluent pentane/DCM 2/1. Detection with
GCꢀFID. Isolated as colourless oil ꢀ 40% (65.4 mg). The obtained NMR data was in
agreement with the literature report12j.
1H NMR (600 MHz, CDCl3) δ 2.35 (d, J = 6.8 Hz, 2H), 2.22 – 2.13 (m, 1H), 1.94 – 1.83
13
(m, 2H), 1.73 – 1.64 (m, 2H), 1.64 – 1.55 (m, 2H), 1.35 – 1.25 (m, 2H). C NMR (151
MHz, CDCl3) δ 119.6, 36.4, 32.2, 25.1, 22.9.
2-cyclobutylacetonitrile (20)
Synthesis was accomplished according to the general procedure using RhCl3—3H2O (8.0
mg; 30.4 ꢁmol; 2 mol%), cyclopentanone (113.5 ꢁl; 106.5 mg; 1.5 mmol; 100 mol%),
methanol (800 ꢁl), methyl cyanoacetate (201.1 ꢁl; 225.8 mg; 2.28 mmol; 150 mol%) and
water (54 ꢁl; 54 mg; 3 mmol; 200 mol%). No extraction from water was needed. 84%
GC yield. Purification: column chromatography, eluent pentane/DCM 2/1. Detection with
GCꢀFID. Isolated as colourless oil ꢀ 56% (81 mg). The obtained NMR data was in
agreement with the literature report12k. The product is volatile and can be lost during the
evaporation.
1H NMR (400 MHz, CDCl3) δ 2.67 – 2.56 (m, 1H), 2.40 (d, J = 6.7 Hz, 2H), 2.23 – 2.10
(m, 2H), 1.96 – 1.77 (m, 4H). 13C NMR (101 MHz, CDCl3) δ 118.9, 31.6, 27.4, 23.7,
17.9.
ACKNOWLEDGEMENTS
The work was financially supported by the Russian Science Foundation (grant #
16ꢀ13ꢀ10393). The contribution of the Center for molecule composition studies of
INEOS RAS is gratefully acknowledged.

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ASSOCIATED CONTENT
Supporting Information
1Hꢀ, 13Cꢀ NMR spectra of all compounds and mechanistic details.
NOTES
The authors declare no competing financial interest.
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