Gold catalyzed Heck-coupling of arenediazonium o-benzenedisulfonimides

DOI: 10.1039/c7ob02624b

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Organic and Biomolecular Chemistry p. 295 - 301 (2018)

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Barbero, Margherita

Dughera, Stefano

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Article abstract of DOI:10.1039/c7ob02624b

Diazonium salts, and precisely arenediazonium o-benzenedisulfonimides, have been used for the first time as efficient electrophilic partners in gold catalyzed Heck-coupling reactions. The synthetic protocol was general, easy and gave the target products in satisfactory yields. Mechanistic insights revealed the fundamental roles of the o-benzenedisulfonimide anion as an electron transfer agent thath promotes a radical pathway that does not require the presence of photocatalysts or external oxidants.

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Takeharu Haino et al.

Solvent-induced emission of organogels based on tris(phenylisoxazolyl)

benzene

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Gold Catalyzed Heck-Coupling of Arenediazonium o-

Benzenedisulfonimides

Margherita Barbero ^aand Stefano Dughera^*a

Received 00th January 20xx,

Accepted 00th January 20xx

Diazonium salts, and precisely arenediazonium o-benzenedisulfonimides, have been used for the first time as efficient

electrophilic partners in gold catalyzed Heck-coupling reactions. The synthetic protocol was general, easy and gave the

target products in satisfactory yields. Mechanistic insights revealed the fundamental roles of the anion of o-

benzenedisulfonimide as an electron transfer agent which promotes a radical pathway that does not require the presence

DOI: 10.1039/x0xx00000x

www.rsc.org/

photocatalysts

external

oxidants

partners in palladium-catalysed cross coupling reactions,

including Mizoroki–Heck reactions, Suzuki–Miyaura reactions,

and Stille couplings, and so they have become an effective

alternative to aryl halides.⁸The use of diazonium salts has

some general advantages: they are more reactive, due to the

fact that the diazonium group is a better nucleofuge than

halide or triflate; they are easily available from anilines, no

base or additional ligands are generally needed; they require

mild reaction conditions and short reaction times, and the

coupling products are generally obtained in high yields.

Interestingly, arenediazonium salts have been recently used

as electrophilic reactants in several Au (I) catalyzed arylation

reactions⁹and cross-coupling reactions (i.e. Suzuki,¹⁰

Sonogashira¹¹coupling), usually under fotoredox conditions.¹²

In fact, their capacity to undergo to a single-electron reduction

under visible light and in the presence of photosensitizers

means that they provide aryl radicals which give sequential

oxidative additions onto Au (I) species. The subsequent

reductive elimination from the resulting Au (III) complexes,

produces the desired coupling adducts and regenerates the Au

(I) catalyst.

Introduction

Gold catalysis is considered a fundamental topic in organic

synthesis with several applications in total syntheses of

complex systems, asymmetric syntheses, C-H activation

reactions and C-C bond formation.^1a-dThe high importance of

gold catalysis is attributable to some peculiar qualities of gold

which include good commercial availability, remarkable

stability, functional group and oxygen tolerance, tunability,

minimal use of additive and excellent chemoselectivity.^1e,f

Many of the investigations into the catalytic reactivity of gold

make use of the propensity of cationic Au (I) complexes to

activate alkynes towards nucleophilic addition due to their

large π-acidic character (alkynophilicity).^1gExtensive studies in

this area have been performed and have found that a wide set

of nucleophiles (N, S, O and C nucleophiles) can be added to

alkynes in an intramolecular or intermolecular fashion,

resulting in the formation of new C-C or C-heteroatom

bonds.^1h,i

In recent years several other gold-catalyzed C-C bond-forming

reactions have been reported.²While focusing our attention

on “classical” cross-coupling reactions, it must be stressed that

as Au (I) has the same d¹⁰configuration as Pd (0) and Cu (I),

meaning that it is able to catalyze reactions typically promoted

by Pd (0).³A number of Au (I) (or Au (III) in Suzuki coupling^4a)

complexes have successfully been employed for the Suzuki,⁴

Sonogashira⁵, Stille⁶and Hiyama⁷couplings in high yields and

with high selectivity. It is worth noting that strong oxidants

were normally required in order to facilitate the Au (I)/Au (IIII)

transition in the catalytic cycle.

If gold catalyzed Suzuki and Sonogashira reactions have now

generally become well-established protocols, on the contrary,

gold catalyzed Heck reactions are a topic that has so far

scarcely been studied.¹³In particular, to the best of our

knowledge, arenediazonium salts have never been used as

electrophilic partners in this reaction.

Some of our research has resulted in a large family of dry

diazonium salts, the arenediazonium o-benzenedisulfonimides

(Fig. 1).^14a

Arenediazonium salts have been widely used as electrophilic

Fig 1 Arenediazonium o-benzenedisulfonimides

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photocatalyst was necessary (Table 1, entry 18) and the

The properties of these compounds mean that they have great reaction also occurred in the dark (Table 1, entry 19).

potential in numerous synthetic applications. They are easy to So, we decided to change the gold catalyst and we carried out

prepare and isolate, they are extremely stable, and they can the reaction in the presence of chloro(triphenylphosphine)gold

be stored for an unlimited time. Moreover, they react easily (Table 1, entries 20–30). We tested various solvents and bases

both in water and in organic solvents, and o- at different temperatures and, to our delight, optimal

benzenedisulfonimide (2; Fig 2) can easily be recovered and conditions were found: heating at 35°C with MeCN as a

reused at the end of the reactions.

solvent and CaCO₃as the base (Table 1, entry 23). A

photocatalyst was also unnecessary in this case (Table 1, entry

25) and the reaction also occurred in the dark (Table 1, entry

27). The target 4a was easily separated, by means of a

chromatographic column from three by-products, shown in

Figure 3, namely N-(4-nitrophenyl)-o-benzenedisulfonimide

(9), nitrobenzene (10) and 4,4’-dinitrobiphenyl (11).

Fig 2 o-Benzenedisulfonimide (2)

Exploration into the synthetic potential of these salts, has led

to them giving excellent results, in palladium catalysed

14c,d

coupling reactions, namely Heck reactions,^14bStille,

Suzuki,^14dNegishi

and Sonogashira^14fcouplings and in

14e

couplings with organoindium derivatives.^14g,h

The ever growing use of gold as a catalyst in organic synthesis,

has driven us to enter this fascinanting field. We herein

described the reactivity of said salts

catalyzed Heck reactions (Scheme 1).

1 as partners in Au(I)

Fig 3 By-products

The high yield and simplicity of the procedure encouraged us

to explore the generality and scope of this reaction further,

using different salts

results are shown in Table 2. The Heck couplings of various

salts 1a–k in MeCN, in the presence of

1 and olefines 3a–e (Scheme 1). The

chloro(triphenylphosphine)gold as the catalyst and CaCO₃as

the base, gave the corresponding adducts 4-8 in excellent

yields, under simple and mild reaction conditions. The reaction

was chemoselective; no traces of disubstituted adducts were

detected in the reactions of diazonium salts containing a

bromine or iodine atom, which could potentially react in the

same way as the diazonium group (Table 2, entries 11–15, 34).

The reaction was not affected by electronic effects; adducts 4-

Scheme

Au (I) catalyzed Heck reaction between

arenediazonium o-benzenedisulfonimides 1 and olefines 3a-e

were obtained in satisfactory yields from salts 1 bearing

either electron-donating or electron-withdrawing groups. On

the other hand, the influence of steric hindrance was evident

Results and discussion

both in salts

1 and in crotonaldehyde (3e). Reactions of salts 1

Initially, the model reaction between acrylaldehyde (3a) and 4-

bearing ortho substituents failed (Table 2, entries 26, 28, 29,

nitrobenzenediazonium o-benzenedisulfonimide

(

)

was

30, 32, 33, 34, 36, 37) with the only exception being those

carried out in the presence

carried out with 3b (Table 2, entries 27, 31, 35)

the presence of an α-methyl group reduced drastically the

yields of the reactions carried out with less reactive salts 1b

. Regarding 3e,

[bis(trifluoromethanesulfonyl)imidate] (triphenylphosphine)

gold as the catalyst in order to optimize the reaction

conditions, as reported in Table 1 (entries 1–19). Various

conditions were tested, solvents and/or temperatures were

changed and bases and/or photocatalyst were added. The

desired coupling product, 4-nitrocinnamaldehyde (4a), was

formed under heating at 50°C in MeCN or EtOH. It is worthing

note that only CaCO₃could be used as a base in EtOH (Table

1, entry 10), while various bases were compatible in MeCN

(Table 1, entries 13, 15–19). However the yields were poor and

unsatisfactory. It must be stressed that, interestingly, no

1c and 1d bearing electron donating-group (Table 2, entries

10, 20).

Moreover, the reactions of heteroarene diazonium o-

benzenedisulfonimides 1i-k (Table 2, entries 43, 44), with the

only exception of 1h (Table 2, entries 38–42) also failed.

Finally, it is interesting to highlight that the reactions between

and 3d were highly regioselective: only traces of possible 3-

arylcyclopentenes were detected (Table 2, entries 4, 9, 14, 19,

24, 41). Finally,

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It was possible to recover o-benzenedisulfonimide (

80% yields from all the reactions described above.

recycled for the preparation of further salts , which is

beneficial from economic and ecological point of view.

2) in about

was

Table 1 Trial reactions between acrilaldehyde (3a) and 4-nitrobenzenediazonium o-benzenedisulfonimide (1a

)

Entry

Temp

(°C)

Time

(h)

Solvent

Catalyst

Base

Photocatalyst

Yield (%)

of 4a ^a,b

r.t

r.t.

THF

Ph₃PAuNTf₂

Ph₃PAuCl

NaOH

Na₂CO₃

Cs₂CO₃

CaCO₃

NaOH

CaCO₃

NaOH

Na₂CO₃

CaCO₃

NaOH

Na₂CO₃

Cs₂CO₃

K₂CO₃

K₃PO₄

CaCO₃

Na₂CO₃

K₃PO₄

CaCO₃

Ru(bpy)₃(PF6)₂

THF

DMSO

EtOH

MeCN

EtOH

DMSO

THF

15^c

traces

39^c

84^c,d,e

dark

Ru(bpy)₃(PF6)₂

Ph₃PAuCl

dark

traces

Ph₃PAuCl

Toluene

Ph₃PAuCl

All the reactions were carried out heating at 35°C, under nitrogen flow, with 1 mmol of 1a, 1.5 mmol of 3a, 5 mol% of Au

catalysts, 1 mmol of various bases and 5 mol% of photocactalyst Yields refer to pure and isolated 4a, purified on a silica gel

chromatography column. The eluent was petroleum ether/diethyl ether (9 : 1). ^cHigher amount of base or Au catalysts oh higher

temperatures does not lead to a yield increase.^dAt room temperature the yield of 4a was remarkably lower (45%). ^eWhen the

reaction was carried out in the presence of 1,3-dinitrobenzene (1 mmol, 170 mg) no 4a was formed

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Table 2 Gold catalyzed reactions between 1a-j and 3a-d

Entry Ar in

Time (h)

Products 4-8

and yields (%)^a,b

1a; 4-NO₂C₆H₄

3a;

3b;

3c;

CHO

4a; 84^c

5a; 87

6a; 91

7a; 67

8a;78^d

4b; 72^c

5b; 68

6b; 75

7b; 63

8b; 37^d

4c; 81

5c; 90

6c; 82

7c; 79

8c; 40^d

4d; 77

5d; 91

6d; 89

7d; 81

8d;-^d,e

4e; 82

5e; 87

6e; 90

7e; 69

8e; 76^d

COOEt

C₆H₅

3.5

1b; 4-MeC₆H₄

7.5

6.5

3.5

1c; 4-BrC₆H₄

7.5

1d; 4-MeOC₆H₄

4.5

1e; 3-NO₂C₆H₄

1f; 2-NO₂C₆H₄

5f; 32^d

4.5

6f; traces

1g; 2-MeC₆H₄

5g; 35^d

6g; traces ^d

1h; 2-IC₆H₄

1i;

5h; 28^d

4i; 86

3.5

5i; 91

6i; 84

7i; 64

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8i; 78^d

1j;

1k;

Unless otherwise stated, all the reactions were performed using arenediazonium o-benzenedisulfonimides

1 in MeCN at 35°C

ratio was 1:1.5. ^bYields

under nitrogen flow and in the presence of CaCO₃(1 mmol) and Ph₃PAuCl (5 mol%). The

(1 mmol) :

refer to pure and isolated 4-8, purified from the by-products on a silica gel chromatography column. ^cThe reactions were carried

out using 4-nitrobenzenediazonium tetrafluoroborate or 4-toluenediazonium tetrafluoroborate (1 mmol) instead of 1a or 1b in

two different solvents, namely EtOH and MeCN at 35°C under nitrogen flow and in the presence of CaCO₃(1 mmol) and

Ph₃PAuCl (5 mol%). The tetrafluoroborate (1 mmol) : 3 ratio was 1:1.5. The yield of 4a was 76% carrying out the reaction in EtOH

and 12% in MeCN. The yield of 4b was 25% in EtOH; no 4b was formed in MeCN. ^dThe reaction was performed heating at 50°C in

the presence of CaCO₃(1.5 mmol). The 1 (1 mmol) : 3

ratio was 1:2.^eAfter 24h the reaction was not complete; GC-MS analyses of

the crude residue showed the presence of 8d (MS (EI): m/z = 176 [M]⁺). However, 8d could not be obtained with an adequate

purity.

The copious and homogeneous results collected provide a low yields of target 4a (12%; Table 2, entry 6, note c), whilst no

good basis for some comments on the reaction mechanism. 4b formed (Table 2, entry 6, note c). This means that,

The first and fundamental fact is that this reaction also accordingly to the literature, the aryl radicals necessary for

occurred in the dark and without any photocatalyst. completion of the reaction mainly formed in EtOH and in the

Furthermore, it must be stressed that, gold catalyst is presence of NO₂group in the tetrafluoroborates. On the

absolutely necessary; in fact the reaction carried out under contrary, it is interesting to note that various solvents were

optimal conditions, but without gold catalyst, failed (Table 1, suitable for use with salt 1a (EtOH, MeCN, THF, toluene; Table

entry 26).

1, entries 25, 28–31) and that the yields of 4a and 4b in the

S. Shin¹⁵and coworkers have recently reported an interesting reactions carried out in MeCN with 1a and 1b were both good

study concerning the cross-coupling of vinyl gold derivatives and almost the same (Table 2, entries 1, 6). In order to explain

with diazonium salts under photoredox or thermal conditions. this different reactivity between

1 and corresponding

In fact, they found that the reaction can run in the dark under tetrafluoroborates, we can use an attractive hypothesis

thermal conditons, where arenediazionium tetrafluoroborate presented in two our previous paper (concerning the

decomposed under heating at 60°C In MeOH, forming aryl bromodediazotation^18aand the Sandmeyer reaction^18bof salts

radicals which oxidize the Au(I) catalyst, allowing the coupling

reaction to occur.

) and based on the possibility that the anion of salts

1 could

act by a primary electron donor reagent toward the

In the light of this, we believe that the reaction mechanism of arenediazonium cations, most likely giving rise to the outer-

this Heck coupling may be similar to that proposed by Schin. sphere (or not bonded) electron transfer complex 12 (Fig 4).

First, a reaction was carried out between 1a and 3° in the Such charge transfer would be actively favored in salts

1 (and

presence of 1,3-dinitrobenzene, an excellent electron not in tetrafluoroborates) by the formation of a complex

acceptor. This reaction failed and so we confirmed its where the partner of the aryldiazenyl radical is a species that is

homolytic course by means of this known diagnostic test highly stabilized by resonance (12a, 12b

(Table 1, entry 25 note e).

)

Under Shin conditions, the formations of aryl radicals from

arenediazonium tetrafluoroborate was possible in MeOH at

60°C. In fact , a thorough study on this topic which proves that

the formation of aryl radicals from arenediazonium

tetrafluoroborates is the result of an electron transfer-

homolysis mechanism, promoted by EtOH and followed by

dediazoniation, has been reported in the literature.¹⁶

Moreover, it is also known from the literature that this thermal

reduction of arenediazonium tetrafluoroborates in alcoholic

solvents, producing free-radicals, is favoured in the order of p-

MeO > p-NO₂, p-Br > p-CH₃>H group in the diazonium salts.¹⁷

Fig 4 Electron transfer complex 12

Furthermore, we highlighted that the formation of 12

occurred as in this research, in a variety of solvents, regardless

In our conditions, reacting 3a and 4-toluenediazonium

tetrafluoroborate in EtOH, we obtained 4b in very low yields

(25%; Table 2, entry 6 note c), while good results were

achieved with 4-nitrobenzenediazonium tetrafluoroborate: 4a

was obtaneid in good yield (75%; Table 2, entry 1 note c). On

the other hand, the same reactions, carried out in MeCN gave

of the type of aromatic ring-bonded substituents and even at

room temperature.^18a,bIn the light of this, we believe that the

formation of 12, may explain the homolitic course (partial,

however) of this reaction as shown in Scheme 2.

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In particular, we postulate that the complex 12 interacts with olefins into the Au(III)–Ph bond is a very facile process ^20dand

the Au (I) catalyst, transferring on it an aryl radical; the Au(II) that β-hydride elimination appears as a very easy process for

complex 13 forms. A further oxidation of 13, most likely due to gold(III) alkyl species.”^20e

an electron donated by 1, gives the Au(III) complex 14 and Clearly, in order to confirm this supposed mechanism, other

other diazenyl radicals 12 which contribute to oxidizing the Au evidences are needed. For this purpose, theoretical

(I) catalyst. It is interesting to note that this radical chain, investigations are currently underway.

triggered by Au (I) catalyst interaction with 12, allows the Finally, it must be stressed that other mechanisms could have

oxidation of the Au (I) catalyst to Au (III) to occur, without the been proposed for this coupling reaction, but this is the only

participation of photocatalysts or external oxidants. At this one that allows to explain in a convincing way all the

point, the Au (III) complex 14 is ready to undergo the typical experimental data.

reactions occurring in the Heck coupling catalytic cycle.¹⁹First,

the insertion reaction with

15,^20a,bto Au(III) complex 16 and then a β-H elimination

reaction produces target and Au (III) complex 17. The

3 leads, through Au(III)/π-complex

Conclusions

We have herein proposed a mild, easy and efficient gold

reductive elimination reaction of the latter, in the presence of

CaCO₃, restores the starting catalyst Ph₃PAuCl.

catalyzed

Heck

coupling

arenediazonium

benzenedisulfonimides

The target products

were

generally obtained in satisfactory yields (32 positive examples,

73% average yield). It is worth noting the interesting role that

the o-benzenedisulfonimide anion plays as an electron transfer

agent in enabling a radical pathway that does not require the

presence of photocatalysts or external oxidants. To the best of

our knowledge, arenediazonium salts have been used as

partners in gold catalyzed Heck reaction for the first time in

this paper.

Experimental

General

All the reactions were carried out in oven dried glassware and

under a nitrogen flow. Analytical grade reagents and solvents

were used and reactions were monitored by GC, GC-MS and

TLC. Column chromatography and TLC were performed on

Merck silica gel 60 (70-230 mesh ASTM) and GF 254,

respectively. Petroleum ether refers to the fraction boiling in

the range 40–70 °C. Room temperature is 20 °C. Mass spectra

were recorded on an HP 5989B mass selective detector

connected to an HP 5890 GC with a methyl silicone capillary

column. ¹H NMR and ¹³C NMR spectra were recorded on a

Brucker Avance 200 spectrometer at 200 and 50 MHz

respectively. IR spectra were recorded on an IR Perkin-Elmer

Scheme 2 Hypothesized mechanism

As shown above (Table 1), catalyst type was crucial to the

success of the reaction. In fact, the reaction carried out in the

presence of

[bis(trifluoromethanesulfonyl)imidate]

UATR-two

benzenedisulfonimides

previously by us.^14aThe crude salts

spectrometer.

Dry

were prepared as described

were virtually pure (by ¹H

arenediazonium

(triphenylphosphine) gold led to unsatisfactory results. It is

likely that the strong electron withdrawing group

bis(trifluoromethanesulfonyl)imidate

destabilizes

NMR spectroscopy) and were used in subsequent reactions

without further crystallization. 4-Tolyldiazonium and 4-

nitrobenzenediazonium tetrafluoroborate were prepared as

reported in the literature.²¹All the other reagents were

purchased from Sigma-Aldrich or Alfa-Aesar. Structures and

purity of all the products obtained in this research were

confirmed by their spectral (NMR, MS and IR) and physical

data (reported in Supplementary Information), substantially

identical to those reported in the literature. Yields of the pure

(GC, GC-MS, TLC and NMR) isolated compounds 4-7 are

collected in Table 2. Satisfactory microanalyses were obtained

for all new compounds.

intermediates 13–16, making their formation difficult. Finally

we believe that the by-product 10 shown in Figure 3, may be

a clue to this radical mechanism. It may derive from the

coupling of some of the radicals that form in the reaction

pathway.

An aspect of this hypothesized mechanism is that the

formation of complex 16 requires alkene

insertion into an

from

Au(III)-C bond of 14, followed by a β-H elimination of

16. These processes are not facile at all;^20bhowever evidences

of an alkene insertion into a Au(III)-C bond^20c-dand subsequent

β-H elimination^20d-fwere recently reported. In particular,

Amgoune and Bourissou stated that “migratory insertion of

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In a oven-dried flask and under nitrogen flow, first anhydrous

CaCO₃(100 mg, 1 mmol) and then 4-nitrobenzenediazonium o-

benzenedisulfonimide (1a, 370 mg, 1 mmol) was added to a

solution of acrolein

(

3a,

90 mg, 1.5 mmol) and

chloro(triphenylphosphine)gold (I) (25 mg, 0.05 mmol, 5mol%)

in MeCN (5 ml). The resulting mixture was stirred at 35°C for 6

h; the completion of the reaction was confirmed by the

absence of azo coupling with 2-naphthol. Then, the reaction

mixture was poured into diethyl ether/water (100 mL, 1:1).

The aqueous layer was separated and extracted with diethyl

ether (50 mL). The combined organic extracts were washed

with water (50 mL), dried with Na₂SO₄and evaporated under

reduced pressure. GC-MS analyses of the crude residue

showed 4-nitrocinnamaldehyde (4a, MS (EI): m/z = 177 [M]⁺)

as the major product, besides traces of 4,4’-dinitrobiphenyl

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(

11), MS (EI) m/z = 244 [M]⁺, nitrobenzene (10), MS (EI) m/z =

123 [M]⁺, N-(4-nitrophenyl)-o-benzenedisulfonimide (

) MS

(EI) m/z = 340 [M]⁺The crude residue was purified on a short

column, eluting with petroleum ether/diethyl ether (9:1). The

only isolated product was the title compound (4a, 150 mg,

84% yield). The aqueous layer and aqueous washings were

collected and evaporated under reduced pressure. The tarry

residue was passed through a column of Dowex HCR-W2 ion

exchange resin (1.6 g/1 g of product), eluting with water

(about 50 mL). After removal of water under reduced pressure,

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virtually pure (¹H NMR) o-benzenedisulfonimide

(2) was

recovered (198 mg, 90% yield; mp 192–194 °C. Lit.^14a190–193

°C).

Chem. Sci., 2016,

and A.-L. Lee, Chem. Sci., 2017,

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, 6190; d) V. Gauchot, D. R. Sutherland

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Conflicts of interest

10 a) S. Witzel, J. Xie, M. Rudolph and A. S. K. Hashmi, Adv.

Synth. Catal., 2017, 359, 1522; b) V. Gauchot and A.-L. Lee,

Chem. Commun., 2016, 52, 10163; d) T. Cornilleau, P.

Hermange and E. Fouquet, Chem. Commun., 2016, 52, 10040

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Petersen, H. Chen and X. Shi, Angew. Chem. Int. Ed., 2015,

54, 8772; b) B. Panda and T. K. Sarkar, Chem. Commun.,

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There are no conflicts to declare.

Acknowledgements

This work has been supported by the University of Torino and

the Ministero dell’Università e della Ricerca.

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