IrIII-Catalyzed direct syntheses of amides and esters using nitriles as acid equivalents: A photochemical pathway

Article abstract of DOI:10.1039/d0nj00002g

An unprecedented Ir^III[df(CF₃)ppy]₂(dtbbpy)PF₆-catalyzed simple photochemical process for direct addition of amines and alcohols to the relatively less reactive nitrile triple bond is described herein. Various amides and esters are synthesized as the reaction products, with nitriles being the acid equivalents. A mini-library of different types of amides and esters is made using this mild and efficient process, which uses only 1 mol% of photocatalyst under visible light irradiation (λ = 445 nm). The reaction strategy is also efficient for gram-scale synthesis.

Full text of DOI:10.1039/d0nj00002g

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DOI: 10.1039/D0NJ00002G
LETTER
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IrIII Catalyzed Direct Syntheses of Amides and Esters Using Nitriles
as “Acid Equivalents”: A Photochemical Pathway
Received 00th January 20xx,
Accepted 00th January 20xx
Ranadeep Talukdar*a
DOI: 10.1039/x0xx00000x
Dedicated to Professor Sabyasachi Sarkar on the ocassion of his 70th birthday.
An unprecedented IrIII[df(CF3)ppy]2(dtbbpy)PF6 catalyzed simple photochemical process for direct addition of amines and
alcohols to relatively less reactive nitrile triple bond is described herein. Various amides and esters are synthesized as the
reaction products with nitriles being the “acid equivalent”. A mini-library of different types of amides and esters are made
using this mild and efficient process which uses only 1 mol% of photocatalysts under visible light irradiation (λ = 445 nm).
The reaction strategy is also efficient for gram-scale synthesis.
nitrile and in amines, replacing water (figure 1)11l-p, whereas
some similar strategies do not require metals at all11q-s. The
Introduction
The presence of dense sp electron cloud makes the
nucleophilic functionalization of the nitrile triple bond a
difficult task. For the sake of their activation selective metal
catalysts are deployed often.1 The involvement of PdII in this
regard is noteworthy.2 An alternate direct approach for nitrile
activation can be the addition of organometallics including
Grignard reagents.3 In parallel, few non-metal catalysts are
also used in special cases.4 Several efforts has been spent for
C-radical initiated reaction on nitriles as well.5 On the other
side, amide is always considered as a specially privileged
organic functional group which have utmost importance in our
day-to-day life.6-10 Whether it is the protein in food,6
polyamides in clothing materials7 or adhesives8, bio-active
molecules in life-saving drugs or drug-precursors,9 or
fertilizers10a and herbicides/insecticides10b-e in agriculture, the
surprising omnipresence of amides is truly a matter of
fascination.
reaction of acid halides with amines is definitely a competitive
procedure for amide synthesis, but it often poses problems
like requirement of low temperature, uncontrollable vigorous
reaction giving side products or commercially non-availability
of certain acid chlorides leading to their in situ preparation in
the laboratory11t-v, which amide reactions are generally devoid
of.
Nevertheless, it is surprising that no photochemical approach
towards the rather innocent looking reaction (table 1 scheme)
for the synthesis of amide 3a from 1a has been made till date.
Our ongoing efforts to unleash the “Greener” photochemical
power of IrIII12a-b or RuII12c transition metal complexes led the
present project to discover their photochemical efficiency in
synthesizing amides and esters from nitriles by reaction with
amines or alcohols respectively for the first time. Here nitriles
act as the “acid equivalents”.
Thinking practically, nitriles could be a very popular choice as
starting materials which can be directly converted to
amides,11a-e rather than the other non-nitrile approaches11f-h
for amide synthesis, including photochemistry11i-j,12a. Thus
transformation of nitriles to amides has been adapted by
several enzymatic biotransformation processes as well.11k
Apart from the general metal catalyzed invariable “hydration”
strategies”,11a-e metal catalyzed limited number of advance
methods are available as well which enable a double-fold
access to wide range of amides, with variation in both the
Figure 1 Chronology of metal catalyzed syntheses of amides from nitriles
Results and discussion
When benzyl amine 1a was irradiated under blue light emitting
diodes (λ=445 nm) along with 2 equivalents of CCl3Br in dry
a.Molecular Synthesis and Drug Discovery Laboratory, Centre of Biomedical
Research, Sanjay Gandhi Postgraduate Institute of Medical Sciences, Lucknow-
226014, India.
CH3CN 2a in presence of only
1 mol% photocatalyst
13a-b
IrIII[df(CF3)ppy]2(dtbbpy)PF6
at room temperature under
E-mail: ranadeep@chem.iitkgp.ernet.in
inert atmosphere, isacetamide 3a was formed in 78% yield
within 9 hours (table 1, entry 1). Lowering the amount of
CCl3Br resulted in a decrease of the yield of 3a (entry 2). Using
Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
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Selectfluor instead of CCl3Br gave only 64% yield (entry 3). Linear primary amine n-butyl amine gave acetamide 3c in
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DOI: 10.1039/D0NJ00002G
13c
Using RuII(bpy)3Cl2 as photocatalyst gave slightly lower yield better yield with
a faster reaction rate. Structurally
of the amide (entry 4). Carrying out the reaction under air constrained adamantane-1-amine gave the corresponding
atmosphere or in presence of CFL light instead of blue LEDs acetamide 3d in good 82% yield. Secondary amines pyrrolidine
only gave 27% and 10% yields (entries 5 and 6). Under 5 mol% and 1,4-morpholine also provided amides 3e and 3f in 85% and
Rose Bengal or Eosin-Y photocatalyst with green LED, the 88% yields respectively.
reaction led to only trace amount of product (entries 7 and 8
respectively). Further the use of either basic or acidic additives
also afforded less amount of products than the optimized
condition (entries 9 and 10 respectively). When the reaction
was carried out in complete dark, no reaction was observed
(entry 11). Changing the reaction temperature to 50 °C or 0 °C
could not result any increment in the yield as well (entries 12
and 13). Carrying out the reaction in DCM or in THF in
presence of 4 equivalents of nitrile gave extremely low yield of
3a (entries 14 and 15), therefore carrying out the reaction
under nitrile as solvent was necessary. Lastly, lingering the
reaction time to 3 days under optimized condition resulted in
no better output (table 1, last entry).
Table 2 Substrate studies with different amines for synthesis of acetamides 3a
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aAll yields are isolated yields.
To check the efficiency of the reaction, benzonitrile 2b, when
reacted, gave benzamide 3g in 77% yield with morpholine
(table 3). Other amines like pyrrolidine, diisopropylamine and
dibenzylamine yielded the amides with comparable yields (3h-
Table 1 Yield optimization in photochemical synthesis of acetamide 3a from
acetonitrile
j). N-benzyl ethanolamine yielded 66% of the corresponding
benzamide (3k) and no ester was obtained by the reaction of
benzonitrile with the O-centre of N-benzyl ethanolamine.
Isopropyl amine gave 68% of the product 3l. Benzyl protected
aniline furnished amide 3m with the lowest yield in the table.
Entry Deviation from the Optimized Condition Time (h)
Yield
(%)a
78
40
64
(0.5 mL CH3CN used for 1 mmol of 1a
None
1.0 Equiv. of CCl3Br used
2.0 Equiv. of Selectfluor used instead of 28
CCl3Br
)
1
2
3
9
25
Table 3 Synthesis of different benzamides with benzonitrilea
4
1
Mol%
photocatalyst
Inert atmosphere not maintained
RuII(bpy)3Cl2
used
as 13
70
5
6
72
27
10
24-Watt CFL lamp used instead of blue 72
LEDs
7
8
Green LEDs are used with 5 mol% Rose 72
Bengal photocatalyst
Green LEDs are used with 5 mol% Eosin- 72
Y photocatalyst
Trace
Trace
9
1.0 Equiv. K2CO3 used as base additive
1.0 Equiv. p-TsOH used as acid additive
Reaction carried out in complete dark
Reaction carried out at 50 °C
Reaction carried out at 0 °C
4.0 Equiv. nitrile in DCM solvent
4.0 Equiv. nitrile in THF solvent
None
72
72
72
8.5
72
72
72
72
Trace
20
0
67
44
16
9
10
11
12
13
14
15
16
aAll yields are isolated yields.
Then different nitriles were tested with piperidine. Acetonitrile
and n-pentanonitrile afforded corresponding amides 3n and
3o with 80% and 77% yields respectively (table 4). Amide 3p
resulted through the reaction of cyclohexanecarbonitrile. 3-
Phenylpropanenitrile gave amide 3q in 64% yield. Benzonitrile
yielded benzamide 3r in 72% yield. Highly electron donating or
withdrawing substitutions were well tolerated (3s and 3t).
Moderate yield with 4-NO2 substituted benzonitrile is
attributed to its high reactivity. 4-Pyridinecarbonitrile afforded
the corresponding amide (3u) in 69% yield.
73
aAll yields mentioned are isolated yields.
Having the optimized condition derived, different amines were
reacted with acetonitrile 2a for synthesizing different N-
substituted acetamides and different primary and secondary
amine partners were utilized in this regard (table 2).
Gratifyingly, p-anisidine also yielded the amide product 3b
,
although in lower yield and slow conversion rate due to
delocalization of the free radical inside the aromatic ring.
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aAll yields are isolated yields.
Table 4 Photochemical synthesis of piperidine amides with different nitrilesa,b
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DOI: 10.1039/D0NJ00002G
When benzonitrile 2b was reacted with different alcohols
under the optimized condition, different benzoates (5i ) were
formed (table 6). Aliphatic open chain or cyclic alcohols gave
good to moderate yields of esters (5i ). Halogenated ethyl
benzoates were also synthesized in good yields (5n ). Etheral
alcohols show moderate yields of the corresponding benzoates
5p ). The presence of methoxy group in the benzyl alcohol
-
u
-
m
-
o
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(
-r
gave a little better yield of its benzoate ester (5s vs 5t) under
this condition. Indole N-substituted ethanol also, was suitable
substrate for this photochemical conversion (5u, 75%).
Table 6. Synthesis of benzoates from benzonitrile 2ba
aAll yields are isolated yields. bFor solid nitriles, 0.5 g nitrile was used (for
products 3s, 3t, 3u, 5z and 5aa).
After synthesizing various amides, the author was urged to
observe the reaction outcomes with alcohols. Quite
satisfyingly, when different alcohols
substrates, the corresponding acetate esters
4
were taken as
were formed
5
(table 5). There is no need to introduce their importances, as
esters are as important as amides in sustaining human life and
culture, which are used as drugs,14 polymer materials15 and in
cosmetics industry/perfumery16 for their pleasant odours.
Because of such importance many new synthetic procedures
are developed recently. Besides the nitriles as starting point
(including Pinner reaction),17 the other available methods
involve the reaction of alcohols with acid derivatives18,
oxidative coupling with aldehydes19, acyl azolium
intermediates20 or with enzymatic methods21. Thus, a simple
radical functionalization of nitrile triple bonds for the first time
to obtain esters will be a great enrichment of its synthetic
armoury.
aAll yields are isolated yields.
Butyl esters (5v-5ab) were synthesized using different nitriles
(table 7). Aliphatic acyclic nitriles or cyclic secondary nitrile
displayed smooth conversion with n-butanol giving good yields
of butyl esters 5v-x. Benzyl cyanide gave moderate yield (67%)
the of butyl acetate 5y. Electron rich methoxy substituted
benzonitrile gave ester 5z in 74% yield. In comparison, highly
electron withdrawing 4-NO2 substituted benzoate ester 5aa
was synthesized albeit in low 34% yield from the
The efficient reaction with 2-phenyl ethanol gave 90% yield of
the ester 5a (table 5). Similarly, high yield of ester 5b was
found with 5-phenyl pentanol. Branched and long aliphatic
chained alcohols participated in the reaction quite efficiently
corresponding benzonitrile. Similarly, butyl nicotinate (5ab
)
(5c and 5d). Substituted (menthol) and unsubstituted cyclic
was obtained in 52% yield with 3-pyridine carbonitrile.
secondary alcohols were also acetylated under the reaction
condition (products 5e and 5f). Lastly, unsaturated alcohols
e.g. but-3-yn-1-ol or citronellol were also photochemically
acetylated with CH3CN (5g and 5h respectively). The lower
yields with unsaturated alcohols were probably for the radical
mediated side reactions with the multiple bonds. It is
noteworthy that tertiary alcohols did not give any product.
Table 7. Synthesis of butyl alkanoates from butanol and nitrilesa
Table 5. Photochemical synthesis of acetate esters with acetonitrile 2aa
aAll yields are isolated yields.
An interesting substrate butane-1,4-diol
this reaction protocol as well, to give diester
6
was subjected to
was with nitrile
7
2b in 35% yield after 1 day of irradiation.
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Scheme 1 Synthesis of diester
7 from butane-1,4-diol
7
8
9
With the author’s previous experience from the photochemical
red-ox generation of amides and esters starting from
aldehydes,12a-b a red-ox neutral reaction mechanism can be
drawn as scheme 2 which involves radical12a. It commences
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Scheme 3 Schematic diagram of proposed PCET process occurring in photocatalytic
amidation/esterification
with photo excitation of IrIII
trichloromethyl radical and bromide anion by donating an
electron to CCl3Br (
).12,22 The photooxidized state of IrIV
thus generated is quenched by the amine ( ) or alcohol ( ) to
reduce and regenerate catalyst by a single electron
transfer (SET), unleashing a proton and the amide or oxide
radical . Then “attacks” nitrile substrate to form
imidamide or imidate radical adds to trichloromethyl
radical to form transient species , which upon workup
furnishes amides
(A (B). B in turn makes a
) to IrIII*
D
C
(E)
In order to check the efficiency of the current protocol
1
4
towards a dinitrile, phthalonitrile
8 was reacted with both
E
A
isopropyl amine and isopropanol under the optimized
conditions. The reaction yielded the bis-amide
respectively in moderate yields (scheme 4).
9 and diester 10
F
F
2
G. G
D
H
3
,
9
or esters
5
,
7
,
10 depending on
F
. Although
.
there is a finite possibility for the CCl3 radical
D
to abstract H
, while the IrV oxidizing
. In that case there will be bromine in place of
.CCl3 in intermediate
radical from amines or alcohols to give
intermediate
F
G
H
. But the end bi-products will be the Scheme 4 Photochemical synthesis of bis-amide 9 and diester 10 from dinitrile 8
same HBr and the unstable CCl3OH.
Two scale-up reactions were carried out to check the efficiency
of this project towards gram-scale syntheses. With acetonitrile
2a, morpholine and 2-phenylethanol provided amide 3f and
ester 5a in 81% and 84% yields respectively (scheme 5).
Scheme 2 Mechanism for IrIII photocatalyzed formation of amides (
3,9) and
esters (5,7,10) from nitriles under blue LED irradiation
Scheme 5 Gram-scale synthesis of amide 3f and ester 5a from nitrile 2a
A simultaneous “Proton Coupled Electron Transfer” (PCET)
process is also likely to be occurring in parallel to the proposed
mechanism in scheme 2 (scheme 3).23 First a proton transfer
occurring between the amine or alcohol and CCl3Br radical
Conclusions
In this project a photocatalytic facile synthesis of amides by
the addition of amine radicals to nitriles is described. The
reaction occur at room temperature under blue LED irradiation
anion (
with the protonated radical of CCl3Br (
from the anion to IrIV will make an amine/alcohol radical along
with IrIII
). In another pathway, could give rise to an
amine/alcohol radical cation by electron transfer process from
it to IrIV giving
. Which and are interconvertible by a single
proton transfer process from amine/alcohol radical cation to
bromide. During the multisite PCET could directly transform
to by the synchronized transfer of a proton from free
I) could generate the amine/alcohol anion along with
in
presence
of
only
1
mol%
photocatalyst
J
). An electron transfer
Ir[df(CF3)ppy]2(dtbbpy)PF6. The addition of alkoxide radicals to
nitriles furnish the corresponding esters. Diol gives diester and
dinitrile forms bis-amide and diester respectively. This is the
first report of photochemical nucleophilic functionalization of
nitrile triple bonds by N/O radicals. The reaction strategy is
also applicable for gram-scale synthesis with almost similar
efficiency. Further mechanistic studies and theoretical studies
on the proposed PCET process are in progress.
(K
I
L
K
I
K
amine/alcohol to CCl3Br giving CCl3 radical and hydrogen
bromide and transfer of an electron from CCl3Br radical cation
to IrIV.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
The author would like to thank DST-SERB, India (grant number
PDF/2018/000072/CS) for financial support.
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