Synthesis of Aliphatic Amides through a Photoredox Catalyzed Radical Carbonylation Involving Organosilicates as Alkyl Radical Precursors

Article abstract of DOI:10.1002/adsc.202000314

Alkyl radicals, from primary to tertiary, formed by photocatalyzed oxidation of organosilicates, are involved efficiently in radical carbonylation with carbon monoxide (CO), in the presence of various amines and CCl₄, leading to a variety of amides in moderate to good yields. (Figure presented.).

Full text of DOI:10.1002/adsc.202000314

Title: Synthesis of Aliphatic Amides through a Photoredox Catalyzed
Radical Carbonylation Involving Organosilicates as Alkyl Radical
Precursors
Authors: Alex Cartier, Etienne Levernier, Anne-Lise Poquet, Takahide
Fukuyama, Cyril Ollivier, Ilhyong Ryu, and Louis Fensterbank
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.202000314
Link to VoR: https://doi.org/10.1002/adsc.202000314

Advanced Synthesis & Catalysis
10.1002/adsc.202000314
FULL PAPER
DOI: 10.1002/adsc.202000314
Synthesis of Aliphatic Amides through a Photoredox Catalyzed
Radical Carbonylation Involving Organosilicates as Alkyl
Radical Precursors
‡
,a
‡,b
b
,a
Alex Cartier, Etienne Levernier, Anne-Lise Dhimane, Takahide Fukuyama,*
,
b
,a,c
,b
Cyril Ollivier,* Ilhyong Ryu,* and Louis Fensterbank*
a
Department of Chemistry, Graduate School of Science, Osaka Prefecture University, Sakai, Osaka 599-8531, Japan
E-mail: fukuyama@c.s.osakafu-u.ac.jp; ryu@c.s.osakafu-u.ac.jp
Sorbonne Université, CNRS, Institut Parisien de Chimie Moléculaire, 4 place Jussieu, CC 229, F-52252 Paris cedex 05,
Paris, France
E-mail: cyril.ollivier@sorbonne-universite.fr; louis.fensterbank@sorbonne-universite.fr
Department of Applied Chemistry, National Chiao Tung University, Hsinchu, Taiwan
E-mail: ryu@c.s.osakafu-u.ac.jp
b
C
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.((Please
delete if not appropriate))
Abstract. Alkyl radicals, from primary to tertiary, formed by photocatalyzed oxidation of organosilicates, are involved
efficiently in radical carbonylation with carbon monoxide (CO), in the presence of various amines and CCl
variety of amides in moderate to good yields.
4
, leading to a
Keywords: Carbonylation; multi-component reaction; photooxidative catalysis; radical/polar; silicates
monoxide (CO) can be incorporated to install a
carbonyl function through the formation of acyl
Introduction
[11,12]
radical intermediates.
photoredox catalyzed carbonylation of alkyl
bis)catecholatosilicates by using 1,2,3,5-
tetrakis(carbazol-9-yl)-4,6-dicyano-benzene
4CzIPN) as photocatalyst and in the presence of
Recently, we reported a
Visible-light photoredox catalysis has changed the
scene of radical chemistry[
1,2]
by notably involving
(
new reactants. Among them, a class of relatively low
oxidation potential of alkyl (bis)catecholatosilicates[
have recently proven to be efficient radical precursors,
as shown by some of us and Molander as well as
other groups.[6] They are interesting for their ease of
3]
(
[4]
[5]
alkenes and allylsulfones which leads to of variety of
functionalized ketones and represents one of the first
radical carbonylation under
a
photooxidative
synthesis from the corresponding alkoxysilane or
trichlorosilane and for their ability to generate
regime.[13] Aiming at extending this process to
trivalent derivatives, we examined the possibility to
develop a new synthesis of aliphatic amides.
Carbonylative synthesis of aliphatic amides has been
achieved by radical/ionic or radical/transition metal
hybrid carbonylation of alkyl iodides (Scheme 1, eq
unstabilized
primary alkyl
radicals,
under
photoredox-catalyzed conditions, whether in the
presence of classical Ru(II) or Ir(III) photocatalysts
or even with an organic dye.[4a-c] The nucleophilic
radicals thus formed can be readily engaged in C-C
bond formation by addition to various species such as
[
14,15]
1
).
radicals by homolytic substitution, we surmised that
adding a chlorinating agent like CCl could in situ
generate acyl chlorides which would then react with
Based on the known halogenation of acyl
[4d]
[4d]
[7]
activated alkenes , allylsulfones,
imines or
recently heteroarenes[ and N-acylhydrazone[9] or by
8]
4
nickel catalyzed cross coupling reactions.[4d,5,6a,6c]
[16]
an amine to lead to amides (Scheme 1, eq 2). We
herein report that various aliphatic amides could
Multicomponent radical reactions have great
potential in organic synthesis,[
10]
in which carbon
1
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Advanced Synthesis & Catalysis
10.1002/adsc.202000314
indeed be synthesized from alkylsilicates under mild
visible-light irradiation in metal-free conditions using
work (Table 1, entry 7) but remained less efficient
than CCl
4
. Although KH
2
PO is not required for the
4
4CzIPN photocatalyst and carbon tetrachloride as a
reaction to occur, it was found to increase
mediator.
significantly the yield of the reaction (Table 1, entry
1
8). H NMR data also shown that the reaction is
Previous Work: Synthesis of Aliphatic Amides via Atom Tranfer Carbonylation
of Alkyl Iodides[14]
cleaner in the presence of KH
2
PO , avoiding the
4
formation of small amounts of undesired by-products.
radical initiator
O
(1)
R1
I
+
CO
+
HNR2R3
R1
NR2R3
Table 1. Optimization of the reaction conditions [a]
R1 = alkyl; R2, R3 = H, alkyl, aryl
This Work: Synthesis of Aliphatic Amides via Photoredox Catalyzed Carbonylation
of Alkyl Silicates
photocatalyst
O
visible light
R1 [Si]
+
CO
+
HNR2R3
(2)
R1
NR2R3
mediator: CCl4
R1 = alkyl; R2, R3 = H, alkyl, aryl
CO
atm)
Time Yield
(h)
Entry Catalyst Donor Solvent
(
3a[b]
Scheme 1. Previous and present concepts for synthesis of
aliphatic amides based on radical carbonylation
1
2
3
4
5
6
7
8
4CzIPN none
DMF
DMF
DMF
DMF
THF
THF
THF
THF
80
80
80
40
80
80
80
80
24
< 5%
24%
15%
20%
51%
4CzIPN CCl
[Ir][c]
CCl
4CzIPN CCl
4CzIPN CCl
4CzIPN CCl
4
4
4
4
4
24
24
24
24
48
48
48
Results and Discussion
[
d]
81%
75%
52%
We chose to test the desired formation of amide
using cyclohexyl bis(cathecolato)silicate 1a in the
presence of isopropylamine 2a, CO, and 4CzIPN as
photocatalyst in a series of model experiments. The
latter were carried out in a stainless-steel autoclave
equipped with two quartz glass windows that serve as
a pressure-durable apparatus during light irradiation
4CzIPN CBrCl
4CzIPN CCl
3
[
e]
4
[
a]
Conditions: potassium [18-Crown-6] bis(catecholato)-
cyclohexylsilicate (1a, 0.3 mmol, 1 equiv), isopropylamine
2a, 2 equiv), photocatalyst (1 mol%), KH PO (1.2 equiv),
(
2
4
CO (40-80 atm), solvent (7 mL), irradiation by blue LED
lamp (425 nm) for 24-48 h. [b] Determined by 1H NMR using
acetanilide
[Ir(dF(CF )ppy) (bpy)](PF ).
(
15 W blue LED, see Supporting Information for
[c]
as
an
internal
standard.
[
d]
Isolated yield. [e] Without
details). The results are summarized in Table 1. Our
3
2
6
first attempt consisted of the irradiation of 1a, 2a,
2 4
KH PO .
4
CzIPN (1 mol%) and KH
2
PO (1.2 equiv) in DMF
4
under a CO pressure of 80 atm during 24 h. While
expected amide 3a was obtained in less than 5%
(
Table 1, entry 1), a significant improvement of the
yield of 2a up to 24% was observed in the presence
of CCl , which would work as chlorine atom donor
and mediator of the reaction (Table 1, entry 2). The
reaction using [Ir(dF(CF )ppy) (bpy)](PF as
4
[
17]
These promising results in hands, we applied this
protocol to a series of alkyl bis(catecholato)silicates 1
and results are summarized in Scheme 2. Similar to
cyclohexyl silicate 1a, cyclopentyl silicate 1b, gave
3
2
6
)
photocatalyst gave 3a in 15% yield (Table 1, entry 3).
When the reaction was carried out under a lower CO
pressure (40 atm), the yield was decreased to 20%
(
Table 1, entry 4). The use of the less nucleophilic
solvent THF instead of DMF improved the yield of
a to 51% (Table 1, entry 5). To our delight, with a
3
longer reaction time of 48 h, we were able to obtain
the product 3a in 81% yield (Table 1, entry 6).
CBrCl , a bromine atom donor, was also found to
3
2
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Advanced Synthesis & Catalysis
10.1002/adsc.202000314
substituted by a pentafluorobenzene ring 1h furnished
the corresponding amide 3h in 59% yield while
perfluorohexyl-substituted ethyl silicate 1g also gave
the corresponding amide, albeit in low yield (34%).
The amide product 3i, bearing a nitrile functionality,
was also obtained in low yield (31%). When the
reaction of 5-hexenyl silicate 1j was tested, an
equimolar mixture of amides, uncyclized 3j and
cyclized 3j’, were obtained in 47% total yield, which
is consistent with our previous report on ketone
synthesis.[13]
We then investigated the viability of a larger scope
of nucleophile amines in this carbonylative amide
synthesis. The results are also summarized in Scheme
2. The reaction of 1a with the primary amine n-
butylamine provided the desired amide 3k in 36%
yield and no double acylation was observed. This
yield could be increased to 56% by using 5 equiv of
n-butylamine. In the case of 2-aminoethanol as
nucleophile, amide 3l was obtained in 51% yield as
the sole product. Of note, no addition of the less
nucleophilic alcohol to form the corresponding ester
was observed. Amide 3m was obtained in 49% yield
from 1a and 2-phenylethylamine. We also checked if
the reaction could occur when using a secondary
amine. The reaction of di-n-propylamine with
cyclohexylsilicate 1a furnished amide 3n in good
yield (61%). More modest yields were obtained from
morpholine (3o, 42%) and aniline (3p, 34%).
Interestingly, however, the yield was substantially
increased up to 84% of desired amide 3q when the
more nucleophilic N-methylaniline was used instead.
In the case of the N-allyl-substituted aniline, the
reaction was even more successful, leading to amide
3
r in an excellent yield of 89%.
Scheme 2. Scope of the multicomponent reaction leading
to amides 3
[13]
Based on our previous study
reports,
and literature
a plausible mechanism is proposed on
[12,16]
Scheme 3. The preliminary step is the excitation of
the photocatalyst 4CzIPN by blue LED light.
the corresponding amide 3b in 77% yield. Even the
highly hindered tert-butyl silicate 1c gave the
corresponding amide 3c in a satisfactory yield of 56%.
The reaction of primary alkyl silicates 1d and 1e gave
[18]
4CzIPN* has a long lifetime at the excited state
(
(
5.1 s) and is also a very good oxidant
.
-
E
1/2(4CzIPN*/[4CzIPN] )
=
+1.59
V
vs.
3d and 3e in 78% and 61% yield, respectively.
[4b,19,20]
SCE),
transfer from organosilicates (Eox < 1 V vs. SCE)
to generate the reduced dye [4CzIPN] and, after
homolytic cleavage of the Si-C bond, the radical
intermediate A.[4-8] C-centered radical A would react
with CO to form the corresponding acyl radical B,
which allows efficient single electron
Knowing from these results that primary, secondary,
and tertiary alkyl silicates worked well for this
reaction, we next focused on the compatibility of
various functional groups toward this process. The
reaction of 1f, bearing a sensitive epoxy ring was
well tolerated and delivered a good yield of the
corresponding amide 3f (73%). A propyl silicate
[4d]
.
-
which after chlorine abstraction from CCl
4
, generates
3
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Advanced Synthesis & Catalysis
10.1002/adsc.202000314
acyl chloride C in situ and radical intermediate D. An
1
acyl chloride of type C was detected by H NMR in
the crude product of a reaction using n-hexyl silicate
1
d and conducted in the regular conditions except no
amine was present.[
21]
Acyl chloride C is then trapped by the amine to
1
form the desired amide 3. Furthermore, H NMR
monitoring of the crude mixture showed a chloroform
.
-
peak suggesting us that [4CzIPN] reduces radical D
to its anionic form E, allowing as well the
regeneration of the photocatalyst 4CzIPN in its
Scheme 4. Synthesis of N-phenyl--butyrolactam 4 from 3-
ground state, and E would be protonated by KH
2
PO
4
(
phenylamino)propane silicate 1k.
or by the protonated amide to form chloroform as by-
product.
Conclusion
In summary, we have achieved a metal-free
synthesis of aliphatic amides from a photoredox-
catalyzed radical carbonylation of alkylsilicates with
CO in the presence amines, in which CCl works as
4
excellent mediator. Thanks to the use of a wide range
of alkyl bis(catecholato)silicates and amines, a large
scope of aliphatic amides could be obtained in a
multicomponent process. We are now examining the
feasibility of the formation of other acyl derivatives
under photooxidative regimes as well as other
multicomponent reactions.
Experimental Section
Please see the Supporting Information for general
experimental considerations.
Typical procedure for the synthesis of silicates 1
Scheme 3. Proposed mechanism
To a stirred solution of catechol (10.05 mmol, 1.11 g) in
dry methanol (20 mL) was added 18-C-6 (5.00 mmol, 1.32
g). After dissolution of the crown ether, the
trimethoxycylohexylsilane (5.09 mmol, 1.04 g) was added,
followed by a 30% solution of potassium methoxide in
methanol (5.05 mmol, 1.18 g). The reaction mixture was
stirred for 3 hours and the solvent was removed under
reduced pressure. The residue was dissolved in the
minimum volume of acetone and diethyl ether was added
until a cloudy solution was obtained (scrapping on the edge
of the flask could be done to induce crystallization). The
flask was placed at -20°C overnight. The crystals were
collected by filtration, washed with diethyl ether and dried
under vacuum to afford silicate 1a (2.44 g, 77%) as a light
brown solid.
We then applied the present protocol to study the
inter- vs intramolecular competition in the amide
formation. Interestingly, when we used aniline
bearing silicate 1k in the presence of 2 equiv of
isopropylamine 2a, the intramolecular reaction
occurred preferentially and only the pyrrolidinone 4
was obtained in 68% yield (Scheme 4).
Synthesis of 4CzIPN
The 4CzIPN has been synthesized following a previous
1
reported procedure. To a 100 mL flask was added NaH
(
60% in mineral oil) (15.0 mmol, 606 mg) in THF (40 mL).
Carbazole (10.0 mmol, 1.68 g) was added slowly to the
mixture. After 30 min of stirring at room temperature the
tetrafluoroisophtalonitrile (2.00 mmol, 406 mg) was added
4
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Advanced Synthesis & Catalysis
10.1002/adsc.202000314
and the mixture was stirred at room temperature for 20
hours. A brown/yellow precipitate progressively appeared.
The solid was successively washed with water and ethanol.
The crude product was dissolved in the minimum of
3
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,
20, 7125-7130; f) S. J. MacCarver, J. X. Qiao, J.
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CH
2 2
Cl and crystallized by addition of hexane to give
4
CzIPN as a yellow solid (1.17 g, 74% yield).
Typical procedure for the photoredox-catalyzed
radical carbonylation of silicates with amines
2
017, 129, 746-750; g) M. O. Akram, P. S. Mali, N.
In a stainless-steel autoclave was added potassium [18-
T. Patil, Org. Lett., 2017, 19, 3075-3078; h) M.
Daniel, G. Dagousset, P. Diter, P.-A. Klein, B.
Tuccio, A.-M. Goncalves, G. Masson, E. Magnier,
Angew. Chem., 2017, 56, 3997-4001 ; Angew. Chem.,
crown-6] bis(catecholato)-cyclohexylsilicate 1a (0.301
2 4
mmol, 189.7 mg), KH PO (0.370 mmol, 50.4 mg) and
4
CzIPN (1mol%, 0.003 mmol, 2.5 mg). THF was added
(
14 mL), followed by isopropylamine (0.595 mmol, 51 L)
and carbontetrachloride (0.455 mmol, 44 L). The
autoclave was flushed 3 times under CO atmosphere and
the reaction mixture was irradiated with blue LEDs (425
nm) under 80 bar CO pressure at r.t. during 48 h. The
reaction was diluted with diethyl ether (50 mL), washed
2
017, 129, 4055-4059; i) L. Candish, M. Freitag, T.
Gensch, F. Glorius, Chem. Sci., 2017, 8, 3618-3622;
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2 3
with an aqueous saturated K CO solution (20 mL x 2
times), water (20 mL x 2 times), dried over MgSO4 and
evaporated under reduced pressure. The crude
1835; k) C. C. Nawrat, C. R. Jamison, Y. Slutskyy,
product
was
purified
to
afford
N-
D. W. C. MacMillan, L. E. Overman, J. Am. Chem.
Soc. 2015, 137, 11270-11273; l) W. Guo, L.-Q. Lu,
Y. Wang, Y.-N. Wang, J.-R. Chen, W.-J. Xiao,
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isopropylcyclohexanecarboxamide 3a (41.6 mg, 82%) as a
yellow solid.
Acknowledgements
This work was supported by the Grant-in-Aid for Scientific
Research (B) (No. 19H02722) and (C) (No. 17K05866) from the
JSPS, and Scientific Research on Innovative Areas 2707: Middle
molecular strategy (No. JP15H05850) from the MEXT. We thank
Sorbonne University, ANR-17-CE07-0018 HyperSilight (PhD
grant to E.L.). IR thanks MOST, Taiwan for generous funding.
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Advanced Synthesis & Catalysis
10.1002/adsc.202000314
FULL PAPER
Synthesis of Aliphatic Amides through a
Photoredox Catalyzed Radical Carbonylation
Involving Organosilicates as Alkyl Radical
Precursors
Adv. Synth. Catal. Year, Volume, Page – Page
Alex Cartier, Etienne Levernier, Anne-Lise
Dhimane, Takahide Fukuyama,* Cyril Ollivier,*
Ilhyong Ryu,* and Louis Fensterbank*
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Advanced Synthesis & Catalysis
10.1002/adsc.202000314
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